Mechanical properties of blended polyethylene (PE) containing the antioxidant Irganox 1010 and the UV-absorber Tinuvin 326 were studied for future use as radiation capsule material for the TRIGA Mark II research reactor. High density and low density polyethylene were blended with the additives and tested for elongation at break, impact strength and gel content, before and after irradiation inside the nuclear reactor. Characterization via FTIR as well as determination of crystallization and melt transition temperatures through DSC were also conducted. It was found that the addition of the antioxidant at different amounts (from 0 to 4 phr) had various effects on the properties of the blended PE, with 0 phr being the amount at which there was the biggest increase in elongation at break and impact strength, post-irradiation.
The electron-phonon coupling constant of the copper oxide-based high temperature superconductors in the van Hove scenario was calculated using three known models and by employing various acoustic data. Three expressions for the transition temperature from the models were used to calculate the constants. All three models assumed a logarithmic singularity in the density of states near the Fermi surface. The calculated electron-phonon coupling constant ranged from 0.06 to 0.28. The constants increased with the transition temperature indicating a strong correlation between electron-phonon coupling and superconductivity in these materials. These values were smaller than the values estimated for the conventional three-dimensional BCS theory. The results were compared with previous reports on direct measurements of electron-phonon coupling constants in the copper oxide based superconductors.
This study investigated the thermal properties of three room temperature curing adhesives containing nano particles which were thixotropic and shear thinning which allowed injection into overhead holes when exposed to different environmental conditions. Viscosity and shear stress of the adhesives were measured as a function of shear rate. The thermal behaviour of the adhesives were measured using dynamic mechanical thermal anylisis following exposures to different temperatures and humidities which included temperatures of 20 degrees Celcius, 30 degrees Celcius and 50 degrees Celcius, relative humidities of 65% RH, 75% RH 95% RH soaked in water at 20 degrees Celcius and placed in the oven at 50 degrees Celcius. The dynamic thermal properties reported include storage and loss modulus, the loss tangent and the glass transition temperature ( Tg ). For nano- and micro-particles filled adhesives, the Tg increased with the temperature increase, even though the adhesives was subjected to high humidity and this was due to further cross-linking. The results showed that room temperature cured epoxies were only partially cured at room temperature.
The current study presents about the effect of cellulose nanofibers (CNFs) filler on the thermal and dynamic mechanical analysis (DMA) of epoxy composites as a function of temperature. In this study hand lay-up method was used to fabricate CNF reinforced Epoxy nanocomposites with CNF loading of 0.5%, 0.75%, and 1% into epoxy resin. The obtained thermal and DMA results illustrates that thermal stability, char content, storage modulus (E'), loss modulus (E") and glass transition temperature (Tg) increases for all CNF/epoxy nanocomposites compared to the pure epoxy. Thermal results revealed that 0.75% offers superior resistance or stability towards heat compared to its counterparts. In addition, 0.75% CNF/epoxy nanocomposites confers highest value of storage modulus as compared to 0.5% and 1% filler loading. Hence, it is concluded that 0.75% CNFs loading is the minimal to enhance both thermal and dynamic mechanical properties of the epoxy composites and can be utilized for advance material applications where thermal stability along with renewability are prime requirements.
The synergetic effect of nitrogen-rich and CO2-philic filler and polymer in mixed matrix-based membranes (MMMs) can separate CO2 competently. The introduction of well-defined nanostructured porous fillers of pores close to the kinetic diameter of the gas molecule and polymer matrix compatibility is a challenge in improving the gas transportation characteristics of MMMs. This study deals with the preparation of porphyrin filler and the polysulfone (PSf) polymer MMMs. The fillers demonstrated uniform distribution, uniformity, and successful bond formation. MMMs demonstrated high thermal stability with a glass transition temperature in the range of 480-610 °C. The porphyrin filler exhibited microporous nature with the presence of π-π bonds and Lewis's basic functionalities between filler-polymer resulted in a highly CO2-philic structure. The pure and mixed gas permeabilities and selectivity were successfully improved and surpass the Robeson's upper bound curve's tradeoff. Additionally, the temperature influence on CO2 permeability revealed lower activation energies at higher temperatures leading to the gas transport facilitation. This can be granted consistency and long-term durability in polymer chains. These results highlight the unique properties of porphyrin fillers in CO2 separation mixed matrix membranes and offer new knowledge to increase comprehension of PSf performance under various contents or environments.
The main goal of the present work was to assess the mechanism of crystallisation, more precisely the dominant component responsible for primary crystal formations and fat agglomerations. Therefore, DSC results exhibited significant effect on temperature transition; peak sharpness and enthalpy at palm stearin (PS) levels more than 40wt.%. HPLC data demonstrated slight reduction in the content of POO/OPO at PS levels less than 40wt.%, while the excessive addition of PS more than 40wt.% increased significantly PPO/POP content. The pNMR results showed significant drop in SFC for blends containing PS less than 40wt.%, resulting in low SFC less than 15% at body temperature (37°C). Moreover, the values of viscosity (η) and shear stress (τ) at PS levels over 40wt.% expressed excellent internal friction of the admixtures. All the data reported indicate that PPO/POP was the major component of primary nucleus developed. In part, the levels of PS should be less than 40wt.%, if these blends are designed to be used for margarine production.
The aim of this study was to evaluate the mechanical properties and glass transition temperature (Tg) of a denture base material prepared from high molecular weight poly methyl methacrylate (PMMA) and alumina (Al2O3). The glass transition temperature was studied by using differential scanning calorimetry (DSC). The effect of powder-to-liquid ratio was investigated. The result showed that the tensile properties and the Tg were slightly effected by the powder-to-liquid ratio. The ratio of 2.2:1 by weight of powder to liquid was found to be the best ratio for mixing the material to give the best result in this formulation.
The aim of this work was to characterize the natural low transition temperature mixtures (LTTMs) as promising green solvents for biomass pretreatment with the critical characteristics of cheap, biodegradable and renewable, which overcome the limitations of ionic liquids (ILs). The LTTMs were derived from inexpensive commercially available hydrogen bond acceptor (HBA) and l-malic acid as the hydrogen bond donor (HBD) in distinct molar ratios of starting materials and water. The peaks involved in the H-bonding shifted and became broader for the OH groups. The thermal properties of the LTTMs were not affected by water while the biopolymers solubility capacity of LTTMs was improved with the increased molar ratio of water and treatment temperature. The pretreatment of oil palm biomass was consistence with the screening on solubility of biopolymers. This work provides a cost-effective alternative to utilize microwave hydrothermal extracted green solvents such as malic acid from natural fruits and plants.
The in situ polymorphic forms and thermal transitions of refined, bleached and deodorized palm oil (RBDPO), palm stearin (RBDPS) and palm kernel oil (RBDPKO) were investigated using coupled X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results indicated that the DSC onset crystallisation temperature of RBDPO was at 22.6°C, with a single reflection at 4.2Å started to appear from 23.4 to 17.1°C, and were followed by two prominent exothermic peaks at 20.1°C and 8.5°C respectively. Further cooling to -40°C leads to the further formation of a β'polymorph. Upon heating, a of β'→βtransformation was observed between 32.1 to 40.8°C, before the sample was completely melted at 43.0°C. The crystallization onset temperature of RBDPS was 44.1°C, with the appearance of the α polymorph at the same temperature as the appearance of the first sharp DSC exothermic peak. This quickly changed from α→β´ in the range 25 to 21.7°C, along with the formation of a small β peak at -40°C. Upon heating, a small XRD peak for the β polymorph was observed between 32.2 to 36.0°C, becoming a mixture of (β´+ β) between 44.0 to 52.5°C. Only the β polymorph survived further heating to 59.8°C. For RBDPKO, the crystallization onset temperature was 11.6°C, with the formation of a single sharp exothermic peak at 6.5°C corresponding to the β' polymorphic form until the temperature reached -40°C. No transformation of the polymorphic form was observed during the melting process of RBDPKO, before being completely melted at 33.2°C. This work has demonstrated the detailed dynamics of polymorphic transformations of PKO and PS, two commercially important hardstocks used widely by industry and will contribute to a greater understanding of their crystallization and melting dynamics.
In this study, poly(ethylene terephthalate) (PET) wastes bottle was recycled by glycolysis process using ethylene glycol. The unsaturated polyester resin (UPR) was then prepared by reacting the glycolysed product with maleic anhydride. The blend of UPR based on recycled PET wastes with liquid natural rubber (LNR) was carried out by varying the amount of LNR from 0 to 7.5 wt%. Mechanical tests such as tensile and impact were conducted to investigate the effects of LNR on the mechanical properties. Scanning Electron Microscopy (SEM) was used to analyze the morphology of the breaking area resulted from the tensile tests on the UPR and blend samples. From the results, the blend of 2.5 wt% LNR in UPR based recycled PET wastes achieved the highest strength in the mechanical properties and showed a well dispersed of elastomer particles in the sample morphology compared to other blends concentrations. This blend sample was then compared to the optimum blend of LNR with commercial resin through the glass transition temperature value Tg, mechanical strength and morphology properties. The comparison study showed that the Tg for UPR based recycled PET was higher than the value represented from commercial resin due to the degree of crystalinity in the molecular structure of the materials. LNR was found to be an effective impact modifier which gave a greater improvement in UPR from recycled PET wastes structure but not to the commercial one which needs 5% LNR to achieve the optimum properties. Thus, the compatibility between the UP resin based recycled PET and LNR was much better than with the commercial resin.
Palm fatty acid distillate (PFAD), is a by-product of the crude palm oil refining process. It comprises mainly of free fatty acids-around 45% palmitic and 33% oleic acids-as the major components. Ultra-violet (UV) curable urethane acrylate (UA) oligomers could be synthesized from PFAD, by the following procedure. A hydroxyl terminated macromer was first prepared by reacting PFAD with a mixture of isophthalic acid, phthalic anhydride, neopentagylcol (NPG), and pentaerythritol. The macromer was then reacted with 2-hydroxylethylacrylate (2HEA) and toluene diisocynate (TDI) to generate a resin, containing acrylate side chains for UV curable application. A series of UA resins were prepared by using 15, 25, 45, 55, and 70% of PFAD, respectively. The UA resin has Mw in the range of 3,200 to 27,000. They could be cured by UV irradiation at an intensity of 225 mW/cm². Glass transition temperature (Tg) of the cured film was measured by differential scanning calorimeter (DSC), and hardness of the film was determined by a pendulum hardness tester, according to American Society for Testing and Materials (ASTM)4366. The resins were used in a wood-coating application. All of the cured films showed good adhesion, hardness, and chemical resistance except for the one using the 70% PFAD, which did not cure properly.
The use of transparent polymers as an alternative to glass has become widespread. However, the direct exposure of these materials to climatic conditions of sunlight and heat decrease the lifetime cost of these products. The aim of this study was to minimize the harm caused by ultraviolet (UV) radiation exposure to transparent poly(methylmethacrylate) (PMMA), which usually leads to changes in the physical and chemical properties of these materials and reduced performance. This was achieved using environmentally friendly cellulose acetate butyrate (CAB). The optical, morphological, and thermal properties of CAB blended with transparent PMMA was studied using UV-VIS spectrophotometry, scanning electron microscopy, X-ray diffraction, dynamic mechanical analysis, and thermal gravimetric analysis. The results show that CAB was able to reduce the effects of UV radiation by making PMMA more transparent to UV light, thereby preventing the negative effects of trapped radiation within the compositional structure, while maintaining the amorphous structure of the blend. The results also show that CAB blended with PMMA led to some properties commensurate with the requirements of research in terms of a slight increase in the value of the modulus and the glass transition temperature for the PMMA/CAB blend.
Solid polymer electrolytes (SPEs) were prepared using rice starch as the polymer, sodium iodide (NaI) as the salt and 1-hexyl-3-methylimidazolium iodide (HMII) as the ionic liquid (IL). The solution casting technique was used for preparation of the PEs. The ionic conductivity and temperaturedependent properties of the PEs were measured and all the SPEs were found to follow the Arrhenius thermal activated model. Ionic conductivity increased as the percentage of ILs increased. The SPE containing 20% (wt) of HMII IL showed the highest ionic conductivity of 1.83×10-3 S/cm. Spectral and structural characterization of the PEs were performed by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD), respectively. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicate that the decomposition temperature (Tdc), glass transition temperatures (Tg) and melting points (Tm) shifted when complexation with HMII occurred. The PEs were used to fabricate dye-sensitized solar cells (DSSCs) and the DSSCs were analyzed under a 1-sun simulator. The SPE with the highest ionic conductivity displayed a short circuit current density (Jsc) of 9.07 (mA cm-2), open circuit voltage (Voc) of 0.58 (V), a fill factor (FF) of 0.65 and had the highest energy conversion efficiency of 3.42%.
In this study, the effects of lignin modification on the properties of kenaf core fiber reinforced poly(butylene succinate) biocomposites were examined. A weight percent gain (WPG) value of 30.21% was recorded after the lignin were modified with maleic anhydride. Lower mechanical properties were observed for lignin composites because of incompatible bonding between the hydrophobic matrix and the hydrophilic lignin. Modified lignin (ML) was found to have a better interfacial bonding, since maleic anhydrides remove most of the hydrophilic hydrogen bonding (this was proven by a Fourier-transform infrared (FTIR) spectrometer-a reduction of broadband near 3400 cm-1, corresponding to the -OH stretching vibration of hydroxyl groups for the ML samples). On the other hand, ML was found to have a slightly lower glass transition temperature, Tg, since reactions with maleic anhydride destroy most of the intra- and inter-molecular hydrogen bonds, resulting in a softer structure at elevated temperatures. The addition of kraft lignin was found to increase the thermal stability of the PBS polymer composites, while modified kraft lignin showed higher thermal stability than pure kraft lignin and possessed delayed onset thermal degradation temperature.
In this work, the optimum filler loading to prepare epoxy/organoclay nanocomposites by the in-situ polymerization method was studied. Bi-functionalized montmorillonite at different filler loading (0.5, 1.0, 2.0, 4.0 wt %) was dispersed in epoxy resin by using a high shear speed homogenizer. The effect on morphology, thermal, dynamic mechanical, and tensile properties of the epoxy/organoclay nanocomposites were studied in this work. Wide-angle X-ray scattering (WAXS) and field emission scanning electron microscope (FESEM) studies revealed that possible intercalated structures were obtained in epoxy/organoclay nanocomposites. Thermogravimetric analysis (TGA) shows that epoxy/organoclay nanocomposites exhibit higher thermal stability at the maximum and final decomposition temperature, as well as higher char content, compared to pristine epoxy. The dynamic mechanical analysis (DMA) indicate that storage modulus (E'), loss modulus (E″), cross-link density and glass transition temperature (Tg) of the nanocomposites were improved with organoclay loading up to 1 wt %. Beyond this loading limit, the deterioration of properties was observed. A similar trend was also observed on tensile strength and modulus. We concluded from this study that organoclay loading up to 1 wt % is suitable for further study to fabricate hybrid nanocomposites for various applications.
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.
Collagen was isolated from threadfin bream (Nemipterus japonicas) waste (mixture of scale and fin) by using 0.5 M citric acid or calamansi juice (Citrofortunella microcarpa) for 12 and 24 hrs at 4°C. The physico-chemical characteristics of the collagens were then compared with the commercial collagen. Shorter extraction time (12 hrs) and extraction using calamansi juice resulted in higher yield. The yield was 22% (12 hrs) and 20.37% (24 hrs) for collagen extracted using calamansi juice and 8.3% (12 hrs) and 6.9% (24 hrs) for collagen extracted using citric acid. Collagen extracted using calamansi juice were light yellow (L = 93.70, a = -1.84, b = 13.44) while citric acid collagens were white (L = 94.82, a = 0.31, b = 0.20). Sensory evaluation on odor recognition test showed that collagen extracted with calamansi juice has a pleasant
natural fragrance which is sweet citrus. Electrophoresis profile indicated that the collagen were of type I comprising of α1 and α2 chains. Threadfin bream collagen contained higher amount of imino acids proline (254.72 to 275.50/1000 residues) and hydroxyproline (7.56 to 13.50/1000 residues) than commercial collagen which is 21.25 and 5.16/1000 residues, respectively. Maximum transition temperature (Tmax) falls within a close range for all the collagens ranging from 24.81 to 25.91°C. Calamansi juice collagens were more viscous compared to others. The extraction of threadfin bream collagen for 12 hrs using calamansi juice generally leads to collagen characterised by pleasant odor, reasonably high yield and more viscous. Therefore, natural source such as calamansi juice could be an alternative medium for collagen extraction.
Redox polymerization of acrylonitrile (AN) with ethyl acrylate (EA) and fumaronitrile (FN), as comonomer and termonomer respectively, were carried out using sodium bisulfite (SBS) and potassium persulphate (KPS) as initiators at 40°C. The actual composition of monomers in copolymers and terpolymers has been characterized by gas chromatography (GC). The effects of EA and FN on the glass transition temperature (Tg) and stabilization temperature have been studied by Differential Scanning Calorimetry (DSC). The degradation behaviour and char yield were obtained by thermogravimetric analysis. Meanwhile, incorporation of 10 mol% of EA in homoPAN system was found to greatly reduce Tg to 66°C as compared to that of the homoPAN (Tg=105°C). The initial cyclization temperature (Ti) was found to be higher (264°C) in comparison to that of homoPAN (246°C). In addition, the incorporation of EA was also shown to reduce the char yield of copolymer to 40%. When FN was incorporated as termonomer, the char yield of poly(AN/EA/ FN) 90/4/6 increased up to 44% after the heat treatment with the lowest Ti (241°C).
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.
A new and efficient method has been designed to prepare 2,2'-arylene-substituted bis(4H-3,1-benzoxazin-4-one) derivatives by using the mixture of cyanuric chloride and N,N-dimethylformamide in a microwave-assisted reaction. The method used and presented here has good rate enhancement and excellent yields.