دو ماهنامه علوم و تکنولوژی پلیمر
سال سی و سوم شماره 1 (پیاپی 165، فروردین و اردیبهشت 1399)

Piezoelectricity can be described as a capability of some particular materials which convert mechanical energy to electrical and vice versa. In addition to ceramics (such as PZT) and polar polymers (PVDF and its copolymers), non-polar cellular polymers have received much attention in the last two decades due to their reasonable price, light weight, flexibility, and piezoelectric coefficient (d33). These polymers are used for a variety of applications, such as energy absorbers, sensors, and the medical sciences. PP, PET, PEN, PE and COP are thermoplastic materials which show high piezoelectric coefficient. By placing these cellular films in a strong electric field (corona discharge or between two electrodes) and in the vicinity of ionizing gas, the gas is ionized by electric field and remains inside the cells, indicating a bipolar moment. Due to the quasi-piezoelectric behavior of these materials, they are called ‘piezoelectrets’ and their properties are called ‘ferroelectricity’. Important factors such as cell structure (morphology, size and density), ionizing gas type, and Young's modulus have direct effect on the piezoelectric coefficient. Furthermore, some post-processing treatments such as chemical and stretching processes improve the piezoelectric properties. Polypropylene is one of the most widely used cellular polymers in the field of piezoelectrics due to features such as reasonable price, good fatigue resistance, and good charge trapping in cells, which has provided a study platform for other polymers. In this review article, we discuss on recent developments in improving piezoelectric coefficient and the work process. The effects of different parameters like electrical breakdown strength of various gases, additives, servicing temperature of polymers and Young's modulus on piezoelectricity in cellular polymers are investigated.

Polymeric fuel tanks have considerably lighter weight in comparison to metal tanks. However, a drastic reduction in evaporation of gasoline vapor from these fuel tanks is needed. The use of nanoparticles to produce polymeric nanocomposites can be an effective way to reduce the extent of permeability and enhance mechanical and processing properties. The planar nanoclay platelets have a substantial potential in enhancement of barrier properties of polymers. It should be noted that the type of compatibilizer plays a remarkable role in the dispersion state of nanoclay.

Nanocomposite samples were prepared using melt blending method in a twin screw extruder. In order to find the optimized formulation, the effects of nanoclay content, compatibilizer type, compatibilizer content and screw speed were assessed using response surface methodology (RSM). The optimization was performed based on the lowest gas permeability, favorable impact strength and melt flow index.

In general, the increment of nanoclay content led to improvement of the barrier properties, while compatibilizer content had an optimal level. The results of optimization revealed that the sample containing 10 wt% of maleic anhydride grafted polyethylene as compatibilizer and 6 wt% of organoclay (Cloisite 20A) possesses the optimum properties. Indeed, this sample showed an optimum balance between different properties and an exfoliated morphology for nanoclay platelets was obtained. On the other hand, although the oxidized polyethylene wax with high viscosity showed the lowest gas permeability, the impact strength and melt flow index were totally undesirable. Nanocomposite samples containing low viscosity oxidized polyethylene wax exhibited the highest gas permeability.

 Thermoplastic polyurethane elastomers are generally synthesized by one of the methods of one-shot, pre-polymer and semi pre-polymer. In the preparation of polyurethanes by these methods the viscosity is increased as the reaction progresses, while the reaction is difficult to control. Therefore, the reaction extrusion method has received much attention in recent years due to high temperature reaction, better mixing of components and more convenient reaction control as well as increased reaction rate due to the elimination of post curing time. The purpose of this study was to study the process parameters of polyurethane elastomer synthesis using reactive extrusion.

Here a prepolymer was synthesized with a polyester polyol (based on adipic acid) and diphenyl methane diisocyanate in a glass reactor. Then butanediol chain extender was added to the prepared prepolymer in a micro extruder at three different temperatures and residence times to obtain the final polymer. FTIR and intrinsic viscosity tests were then taken from 9 prepared samples to determine the optimum temperature and residence time.

The results showed that the temperature of 165°C and the residence time of 10 min were the optimum conditions for the elastomer synthesis through reactive extrusion. Then, by designing three formulations, three thermoplastic elastomer specimens were prepared by adding butanediol chain extender to the prepolymers, in a micro-extruder, and their physical mechanical properties were studied. The results showed that using this method and the obtained process conditions, it is possible to provide polyurethane thermoplastic elastomers with desirable properties in shorter time.

 Recent advances in micro- and nanotechnology have led to possible design of functional micro/nanostructured surfaces with micro/nanotopography features that can exhibit low adhesion properties. An important example of such structures is superhydrophobic surface, which is extremely water repellent. In the present work, the effects of surface microtopography on the wetting of poly(dimethylsiloxane) (PDMS) rubber film with the goal of producing superhydrophobic surface are investigated.

Micropillar arrays inspired by biological structures found in nature are produced on PDMS surface using a soft microlithography technique with different pitch/width ratios. To this end, the masters are fabricated using conventional microfabrication techniques and photolithography. Master designs tested are inverted pillar shape fabricated by anisotropic etching of silicon (reactive-ion etching, DRIE), a high aspect ratio master and a low aspect ratio photoresist master.

Our fabricated pillars have nano-scale ripples that arise from the series of alternating, independent silicon etching and sidewall passivation steps used in the DRIE process. The elastomeric stamps are negative replicas of the masters and they are fabricated by PDMS. The stamps have a regular array of protruding features, in order to make a pattern transfer to the target substrate during m-contact printing. Several pitch/width ratios are configured to optimize the relationship between surface topography and wetting behavior of PDMS film using static water contact angle measurements. We have correlated these structures with PDMS rubber hydrophobicity and have also characterized the transition from the composite (Cassie-Baxter) to wetted (Wenzel) states for different types of surface structures. The surface topography-dependent contact angle of water underwent a transition from Cassie-Baxter to Wenzel states at pitch size ~60 mm.

 Polyglycidyl nitrate (PGN) is used in the manufacture of propellant elastomers due to its properties such as highly energetic composition, high density, high oxygen balance, high explosion enthalpy and suitable compatibility with other components. In addition to its desirable properties, this polymer has disadvantages such as high glass transition temperature, poor mechanical properties, and low content of total solid. Also, its elastomer can undergo decuring process. To remedy these disadvantages, its copolymers are prepared using polymers with optimal thermal and mechanical properties.

In this research an energetic polypropylene glycol/polyglycidyl nitrate/polypropylene glycol (PPG/PGN/PPG) triblock copolymer was synthesized for the first time by cationic ring-opening polymerization of propylene oxide and PGN as macroinitiator, in the presence of boron trifluoride etherate (BF3.OEt2) as the catalyst. The effect of temperature and catalyst content on molecular weight and reaction yield was investigated. The obtained product was characterized by FTIR, GPC, and 1H and 13C NMR spectroscopy. Also, the thermal properties of the copolymer were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

The results showed that by increasing the temperature from 0 to 15°C, the conversion and yield increased. On the other hand, due to the low boiling point of propylene oxide (34°C) and the exothermic reaction, it is impossible to increase the reaction temperature above 15°C. By increasing the catalyst content from 0.2% to 1% by weight of the initiator, the polymer molecular weight increased and the highest yield was achieved in presence of 1% by weight of the catalyst, but by increasing the catalyst content from 1 to 1.5 weight percent, yield and molecular weight have decreased due to the development of adverse reactions. Studies by TGA and DSC showed an increase in thermal stability and a decrease in glass transition temperature of the copolymer compared to PGN.

 Graphene oxide (GO) as an important nanoparticle having unique characteristics and the ability to improve physical and mechanical properties of different biopolymers has been taken into consideration during the last decade.  Thus, in this study, graphene oxide was used for the modification of polymeric films based on chitosan (CS)/gelatin (GL)/polyvinyl alcohol (PVA).

Two series of films with different composition ratios were prepared by solution casting method. Graphene oxide at different concentrations (0, 0.2, 0.4 and 0.8 wt%) was added to the solutions to investigate the effect of PVA and GO amounts on the physical and mechanical properties of the films. The synthesized films were investigated by tensile, swelling, water vapor transmission rate (WVTR), antibacterial and scanning electron microscopy (SEM) tests.

The tensile results showed that the graphene oxide improved the mechanical properties such as tensile modulus and strength, while decreased the elongation-at-break of the prepared samples. The increase in the PVA content of the films led to lower mechanical properties in films. The results of swelling tests at three different (neutral, acidic, and basic) media showed that the PVA led to the decrement of swelling, and higher amounts of GO resulted in a considerable decrease in degree of swelling of the films. The WVTR results showed that the changing in film composition did not considerably change the WVTR of the films, while the GO resulted in a decrease in WVTR of the samples. The antibacterial results showed that adding PVA did not affect the inhibition zone diameter, meanwhile the addition of graphene oxide led to an increase of the inhibition zone diameter. The SEM results showed a uniform distribution of GO nanoparticles within the polymeric films which was due to the compatibility of GO with polymeric matrix.