A flexible solid polymer electrolyte (SPE) system based on poly(ε-caprolactone) (PCL), a FDA approved non-toxic and biodegradable material in the effort to lower environmental impact was prepared. Ammonium thiocyanate (NH4SCN) and ethylene carbonate (EC) were incorporated as the source of charge carriers and plasticizing agent, respectively. When 50wt.% of ethylene carbonate (EC) was added to PCL-NH4SCN system, the conductivity increased by two orders from of 3.94×10(-7)Scm(-1) to 3.82×10(-5)Scm(-1). Molecular vibrational analysis via infrared spectroscopy had been carried out to study the interaction between EC, PCL and NH4SCN. The relative percentage of free ions, ion pairs and ion aggregates was calculated quantitatively by deconvoluting the SCN(-) stretching mode (2030-2090cm(-1)). This study provides fundamental insight on how EC influences the free ion dissociation rate and ion mobility. The findings are also in good agreement to conductivity, differential scanning calorimetry and X-ray diffraction results. High dielectric constant value (89.8) of EC had made it an effective ion dissociation agent to dissociate both ion pairs and ion aggregates, thus contributing to higher number density of free ions. The incorporation of EC had made the polymer chains more flexible in expanding amorphous domain. This will facilitate the coupling synergy between ionic motion and polymer segmental motion. Possible new pathway through EC-NH4(+) complex sites for ions to migrate with shorter distance has been anticipated. This implies an easier ion migration route from one complex site to another.
New environmentally friendly plasticized poly(lactic acid) (PLA) kenaf biocomposites were obtained through a melt blending process from a combination of epoxidized jatropha oil, a type of nonedible vegetable oil material, and renewable plasticizer. The main objective of this study is to investigate the effect of the incorporation of epoxidized jatropha oil (EJO) as a plasticizer and alkaline treatment of kenaf fiber on the thermal properties of PLA/Kenaf/EJO biocomposites. Kenaf fiber was treated with 6% sodium hydroxide (NaOH) solution for 4 h. The thermal properties of the biocomposites were analyzed using a differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). It must be highlighted that the addition of EJO resulted in a decrease of glass transition temperature which aided PLA chain mobility in the blend as predicted. TGA demonstrated that the presence of treated kenaf fiber together with EJO in the blends reduced the rate of decomposition of PLA and enhanced the thermal stability of the blend. The treatment showed a rougher surface fiber in scanning electron microscopy (SEM) micrographs and had a greater mechanical locking with matrix, and this was further supported with Fourier-transform infrared spectroscopy (FTIR) analysis. Overall, the increasing content of EJO as a plasticizer has improved the thermal properties of PLA/Kenaf/EJO biocomposites.
Poly(lactic acid) (PLA)-based nanocomposites filled with graphene nanoplatelets (xGnP) that contains epoxidized palm oil (EPO) as plasticizer were prepared by melt blending method. PLA was first plasticized by EPO to improve its flexibility and thereby overcome its problem of brittleness. Then, xGnP was incoporated into plasticized PLA to enhance its mechanical properties. Plasticized and nanofilled PLA nanocomposites (PLA/EPO/xGnP) showed improvement in the elongation at break by 3322% and 61% compared to pristine PLA and PLA/EPO, respectively. The use of EPO and xGnP increases the mobility of the polymeric chains, thereby improving the flexibility and plastic deformation of PLA. The nanocomposites also resulted in an increase of up to 26.5% in the tensile strength compared with PLA/EPO blend. XRD pattern showed the presence of peak around 26.5° in PLA/EPO/xGnP nanocomposites which corresponds to characteristic peak of graphene nanoplatelets. Plasticized PLA reinforced with xGnP showed that increasing the xGnP content triggers a substantial increase in thermal stability. Crystallinity of the nanocomposites as well as cold crystallization and melting temperature did not show any significant changes upon addition of xGnP. However, there was a significant decrease of glass transition temperature up to 0.3wt% of xGnP incorporation. The TEM micrograph of PLA/EPO/xGnP shows that the xGnP was uniformly dispersed in the PLA matrix and no obvious aggregation was observed.
Coating has been widely used in pharmaceutical manufacture either as non-functional or a functional entity. The objectives of the present study were to investigate the effect of plasticizers such as PEG400, PEG1000 and triacetin on mechanical properties, glass transition temperature and water vapor transmission of free films prepared from HPMC and/or HPMC:PVA blends, to develop suitable coating system for tablets, and to determine the release profiles of the coated tablets. The tensile strength of plasticized HPMC films was generally lower than that of control HPMC film and could be attributed to increased crystallinity and segmental chain mobility of HPMC. This effect increased as the concentration of plasticizer increased. Generally the addition of both grades of polyethylene glycol (PEG400 & PEG1000) increased the moisture permeability of HPMC films but the films containing triacetin provided a more rigid barrier to moisture compared to unplasticized HPMC films. The dissolution profiles of paracetamol tablets coated with 7% w/v HPMC coating-solutions containing PEG400, PEG1000 and triacetin, and those containing PEG400 & PVA together showed that HPMC had weak water resistance. The presence of PEG400 and 1000 in HPMC films further weakened its resistance to solubility while the presence of triacetin caused a little increase in HPMC water resistance. From the results it was concluded that HPMC at 7%w/w concentration was suitable for film-coating intended for non-functional coating. Presence of the PEG 400, PEG1000 and triacetin as well as the presence of PVA and PEG400 together improved the coating properties of HPMC films and made it more suitable as a non-functional coating material.
Starch blend films made from sago and mung bean were prepared by casting with glycerol as the plasticizer and subsequently exposed to ultraviolet (UV) irradiation for 2 h. The films were characterized by thickness, moisture sorption isotherms, X-ray diffraction and Fourier transform infrared (FTIR) spectroscopy. All films produced were colorless while incorporation of glycerol resulted in more flexible and manageable films. Moisture sorption isotherms for all films showed sigmoidal shape and the control films showed slightly higher curve than treated films. While for X-ray analysis, the control and treated films for all formulations showed similar pattern, however for treated films showed more crystalline character. UV radiation showed affect on X-ray diffraction and sorption isotherms; however the UV radiation did not affect the spectra pattern of FTIR.
Starch is a biodegradable polymer produced in abundance from many renewable resources. This study examined the influence of citric acid (0-40% w/wt%) ) and water (0-40% w/wt%) as secondary additive and glycerol as plasticizer on the mechanical properties of bio-plastic starch (BPS) from Malaysian sago. The CA content varies from 0 to 40 w/wt% while water was also varied from 0 to 40 w/wt%. FT-IR spectroscopy showed that acid citric improve the properties of BPS and water give negative effects to the carbon hydrogenbond. It is obvious that the addition of the CA at 30 wt/wt% improve the mechanical property of BPS to more than 40% compare to the addition of water.
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.
In this work, plasticized magnesium ion-conducting polymer blend electrolytes based on chitosan:methylcellulose (CS:MC) were prepared using a solution cast technique. Magnesium acetate [Mg(CH3COO)2] was used as a source of the ions. Nickel metal-complex [Ni(II)-complex)] was employed to expand the amorphous phase. For the ions dissociation enhancement, glycerol plasticizer was also engaged. Incorporating 42 wt% of the glycerol into the electrolyte system has been shown to improve the conductivity to 1.02 × 10-4 S cm-1. X-ray diffraction (XRD) analysis showed that the electrolyte with the highest conductivity has a minimum crystallinity degree. The ionic transference number was estimated to be more than the electronic transference number. It is concluded that in CS:MC:Mg(CH3COO)2:Ni(II)-complex:glycerol, ions are the primary charge carriers. Results from linear sweep voltammetry (LSV) showed electrochemical stability to be 2.48 V. An electric double-layer capacitor (EDLC) based on activated carbon electrode and a prepared solid polymer electrolyte was constructed. The EDLC cell was then analyzed by cyclic voltammetry (CV) and galvanostatic charge-discharge methods. The CV test disclosed rectangular shapes with slight distortion, and there was no appearance of any redox currents on both anodic and cathodic parts, signifying a typical behavior of EDLC. The EDLC cell indicated a good cyclability of about (95%) for throughout of 200 cycles with a specific capacitance of 47.4 F/g.
The polymer electrolyte system of chitosan/dextran-NaTf with various glycerol concentrations is prepared in this study. The electrical impedance spectroscopy (EIS) study shows that the addition of glycerol increases the ionic conductivity of the electrolyte at room temperature. The highest conducting plasticized electrolyte shows the maximum DC ionic conductivity of 6.10 × 10-5 S/cm. Field emission scanning electron microscopy (FESEM) is used to investigate the effect of plasticizer on film morphology. The interaction between the electrolyte components is confirmed from the existence of the O-H, C-H, carboxamide, and amine groups. The XRD study is used to determine the degree of crystallinity. The transport parameters of number density (n), ionic mobility (µ), and diffusion coefficient (D) of ions are determined using the percentage of free ions, due to the asymmetric vibration (υas(SO3)) and symmetric vibration (υs(SO3)) bands. The dielectric property and relaxation time are proved the non-Debye behavior of the electrolyte system. This behavior model is further verified by the existence of the incomplete semicircle arc from the Argand plot. Transference numbers of ion (tion) and electron (te) for the highest conducting plasticized electrolyte are identified to be 0.988 and 0.012, respectively, confirming that the ions are the dominant charge carriers. The tion value are used to further examine the contribution of ions in the values of the diffusion coefficient and mobility of ions. Linear sweep voltammetry (LSV) shows the potential window for the electrolyte is 2.55 V, indicating it to be a promising electrolyte for application in electrochemical energy storage devices.
In the present work, a novel polymer composite electrolytes (PCEs) based on poly(vinyl alcohol) (PVA): ammonium thiocyanate (NH4SCN): Cd(II)-complex plasticized with glycerol (Gly) are prepared by solution cast technique. The film structure was examined by XRD and FTIR routes. The utmost ambient temperature DC ionic conductivity (σDC) of 2.01 × 10-3 S cm-1 is achieved. The film morphology was studied by field emission scanning electron microscopy (FESEM). The trend of σDC is further confirmed with investigation of dielectric properties. Transference numbers of ions (tion) and electrons (tel) are specified to be 0.96 and 0.04, respectively. Linear sweep voltammetry (LSV) displayed that the PCE potential window is 2.1 V. The desired mixture of activated carbon (AC) and carbon black was used to fabricate the electrodes of the EDLC. Cyclic voltammetry (CV) was carried out by sandwiching the PCEs between two carbon-based electrodes, and it revealed an almost rectangular shape. The EDLC exhibited specific capacitance, energy density, and equivalent series resistance with average of 160.07F/g, 18.01Wh/kg, and 51.05Ω, respectively, within 450 cycles. The EDLC demonstrated the initial power density as 4.065 × 103 W/Kg.
The current research trend for excellent miscibility in polymer mixing is the use of plasticizers. The use of most plasticizers usually has some negative effects on the mechanical properties of the resulting composite and can sometimes make it toxic, which makes such polymers unsuitable for biomedical applications. This research focuses on the improvement of the miscibility of polymer composites using two-step mixing with a rheomixer and a mix extruder. Polylactic acid (PLA), chitin, and starch were produced after two-step mixing, using a compression molding method with decreasing composition variation (between 8% to 2%) of chitin and increasing starch content. A dynamic mechanical analysis (DMA) was used to study the mechanical behavior of the composite at various temperatures. The tensile strength, yield, elastic modulus, impact, morphology, and compatibility properties were also studied. The DMA results showed a glass transition temperature range of 50 °C to 100 °C for all samples, with a distinct peak value for the loss modulus and factor. The single distinct peak value meant the polymer blend was compatible. The storage and loss modulus increased with an increase in blending, while the loss factor decreased, indicating excellent compatibility and miscibility of the composite components. The mechanical properties of the samples improved compared to neat PLA. Small voids and immiscibility were noticed in the scanning electron microscopy images, and this was corroborated by X-ray diffraction graphs that showed an improvement in the crystalline nature of PLA with starch. Bioabsorption and toxicity tests showed compatibility with the rat system, which is similar to the human system.
Rice starch is a promising biomaterial for thin film development in buccal drug delivery, but the plasticisation and antiplasticisation phenomena from both plasticisers and drugs on the performance of rice starch films are not well understood. This study aims to elucidate the competing effects of sorbitol (plasticiser) and drug (antiplasticiser) on the physicochemical characteristics of rice starch films containing low paracetamol content. Rice starch films were prepared with different sorbitol (10, 20 and 30% w/w) and paracetamol contents (0, 1 and 2% w/w) using the film casting method and were characterised especially for drug release, swelling and mechanical properties. Sorbitol showed a typical plasticising effect on the control rice starch films by increasing film flexibility and by reducing swelling behaviour. The presence of drugs, however, modified both the mechanical and swelling properties by exerting an antiplasticisation effect. This antiplasticisation action was found to be significant at a low sorbitol level or a high drug content. FTIR investigations supported the antiplasticisation action of paracetamol through the disturbance of sorbitol-starch interactions. Despite this difference, an immediate drug release was generally obtained. This study highlights the interplay between plasticiser and drug in influencing the mechanical and swelling characteristics of rice starch films at varying concentrations.
This paper reports the post-processing ageing phenomena of thermoplastic sago starch (TPS) and plasticised sago pith waste (SPW), which were processed using twin-screw extrusion and compression moulding techniques. Wide angle X-ray diffraction (XRD) analyses showed that after processing, starch molecules rearranged into VH-type (which was formed rapidly right post processing and concluded within 4 days) and B-type (which was formed slowly over a period of months) crystallites. Evidence from Fourier transform infrared spectroscopy (FTIR) analyses corroborated the 2-stage crystallisation process, which observed changes in peak styles and peak intensities (at 1043 and 1026 cm-1) and bandnarrowing. Thermogravimetric analysis (TGA) studies showed that the thermal stability of plasticised SPW declined continuously for 90 days before gradual increments ensued. For all formulations tested, post-processing ageing led to drastic changes in the tensile strength (increased) and elongation at break (decreased). Glycerol and fibres restrained the retrogradation of starch molecules in TPS and SPW.
In this work, a pair of biopolymer materials has been used to prepare high ion-conducting electrolytes for energy storage application (ESA). The chitosan:methylcellulose (CS:MC) blend was selected as a host for the ammonium thiocyanate NH4SCN dopant salt. Three different concentrations of glycerol was successfully incorporated as a plasticizer into the CS-MC-NH4SCN electrolyte system. The structural, electrical, and ion transport properties were investigated. The highest conductivity of 2.29 × 10-4 S cm-1 is recorded for the electrolyte incorporated 42 wt.% of plasticizer. The complexation and interaction of polymer electrolyte components are studied using the FTIR spectra. The deconvolution (DVN) of FTIR peaks as a sensitive method was used to calculate ion transport parameters. The percentage of free ions is found to influence the transport parameters of number density (n), ionic mobility (µ), and diffusion coefficient (D). All electrolytes in this work obey the non-Debye behavior. The highest conductivity electrolyte exhibits the dominancy of ions, where the ionic transference number, tion value of (0.976) is near to infinity with a voltage of breakdown of 2.11 V. The fabricated electrochemical double-layer capacitor (EDLC) achieves the highest specific capacitance, Cs of 98.08 F/g at 10 mV/s by using the cyclic voltammetry (CV) technique.
The specific heats (Csp) of neat polyvinyl alcohol (NPVOH) and 40 phr glycerol plasticized polyvinyl alcohol (PPVOH) were measured using a method known as power compensate differential scanning calorimetry. A high purity sapphire (Al2O3) was used as a reference material. NPVOH has a melting temperature of approximately 480 K, while PPVOH has a value of 30 K lower than NPVOH. The amplitude increment of Csp for NPVOH was also higher than PPVOH at melting stage. Overall, Csp of NPVOH is lower than PPVOH because glycerol has reduced the rigidity of PVOH and subsequently induced the motion of molecular structure at an elevated temperature. Based on the specific heat outcomes, neat PVOH and glycerol plasticized PVOH required 1173.544 J/g and 1946.631 J/g, respectively, to heat from 330 to 550 K.
Antibacterial effect of modified sago starch-alginate edible film incorporating lemongrass oil at various concentrations was studied. Edible films were prepared from a mixture of modified sago starch and alginate. Lemongrass oil (0.1 - 0.4%, v/w) and glycerol (0 and 20%, w/w) were incorporated in the films to act as natural antimicrobial agent and plasticizer, respectively. The films were characterized for antibacterial activity against food pathogenic bacteria such as Escherichia coli O157:H7, Salmonella Enteritidis and Staphylococcus aureus. The edible film exhibited antibacterial activity against Escherichia coli O157:H7 and Salmonella Enteritidis by using agar diffusion assay method. For films tested against Escherichia coli O157:H7, the zone of inhibition increased significantly (p < 0.05) with addition of lemongrass oil at all levels both in the presence and absence of glycerol. The films also significantly (p < 0.05) inhibited the growth of Salmonella enteritidis only with 0.4% lemongrass oil (in the presence and absence of glycerol). However, the films containing lemongrass oil did not show any inhibition effect on Staphylococcus aureus.
Rice starch is known to have an excellent film-forming behaviour in the packaging industry but inadequate attention was given to this biopolymer to be developed into thin films for drug delivery. Accordingly, rice starch thin films containing a model drug, paracetamol and plasticisers (glycerol or sorbitol) were developed using film casting technique. This study focuses on investigating the impact of plasticiser and drug loading on drug release pattern of rice starch films which has not been explored to date. The obtained rice films were characterised for their physicochemical properties including swelling and dissolution study. The highest drug dissolution rate was achieved in the rice films with a low drug loading due to drug amorphicity in nature. When drug loading increases, the swelling behaviour of rice films plays a dominant role in releasing drug in the crystalline form. The role of plasticiser was indicated by the plasticiser-starch interaction where a strong interaction allows drug solubilisation more readily in the dissolution medium. It is envisaged that rice films could be tailored to achieve desired drug release pattern with different plasticiser.
Phthalates have been blended in various compositions as plasticizers worldwide for a variety of purposes. Consequently, humans are exposed to a wide spectrum of phthalates that needs to be researched and understood correctly. The goal of this review is to focus on phthalate's internal exposure pathways and possible role of human digestion on liver toxicity. In addition, special focus was made on stem cell therapy in reverting liver toxicity. The known entry of higher molecular weight phthalates is through ingestion while inhalation and dermal pathways are for lower molecular weight phthalates. In human body, certain phthalates are digested through phase 1 (hydrolysis, oxidation) and phase 2 (conjugation) metabolic processes. The phthalates that are made bioavailable through digestion enter the blood stream and reach the liver for further detoxification, and these are excreted via urine and/or feces. Bis(2-ethylhexyl) phthalate (DEHP) is a compound well studied involving human metabolism. Liver plays a pivotal role in humans for detoxification of pollutants. Thus, continuous exposure to phthalates in humans may lead to inhibition of liver detoxifying enzymes and may result in liver dysfunction. The potential of stem cell therapy addressed herewith will revert liver dysfunction and lead to restoration of liver function properly.
High melting point polymeric carrier without plasticizer is unacceptable for solid dispersion (SD) by melting method. Combined polymer-plasticizer carrier significantly affects drug solubility and tableting property of SD.
Chitosan (CS)-dextran (DN) biopolymer electrolytes doped with ammonium iodide (NH4I) and plasticized with glycerol (GL), then dispersed with Zn(II)-metal complex were fabricated for energy device application. The CS:DN:NH4I:Zn(II)-complex was plasticized with various amounts of GL and the impact of used metal complex and GL on the properties of the formed electrolyte were investigated.The electrochemical impedance spectroscopy (EIS) measurements have shown that the highest conductivity for the plasticized system was 3.44 × 10-4 S/cm. From the x-ray diffraction (XRD) measurements, the plasticized electrolyte with minimum degree of crystallinity has shown the maximum conductivity. The effect of (GL) plasticizer on the film morphology was studied using FESEM. It has been confirmed via transference number analysis (TNM) that the transport mechanism in the prepared electrolyte is predominantly ionic in nature with a high transference number of ion (ti)of 0.983. From a linear sweep voltammetry (LSV) study, the electrolyte was found to be electrochemically constant as the voltage sweeps linearly up to 1.25 V. The cyclic voltammetry (CV) curve covered most of the area of the current-potential plot with no redox peaks and the sweep rate was found to be affecting the capacitance. The electric double-layer capacitor (EDLC) has shown a great performance of specific capacitance (108.3 F/g), ESR(47.8 ohm), energy density (12.2 W/kg) and power density (1743.4 W/kg) for complete 100 cycles at a current density of 0.5 mA cm-2.