Showing papers by "Pijush Ghosh published in 2018"

Comparative Role of Chain Scission and Solvation in the Biodegradation of Polylactic Acid (PLA)

Abstract: The molecular mechanism behind the process of biodegradation and consequently the loss in mechanical properties of polylactic acid (PLA) requires detailed understanding for the successful designing of various technological devices. In this study, we examine the role of free water and chain scission in this degradation process and quantify the mechanical properties of pristine and nanoparticle-reinforced PLA as it degrades over time. The in situ mechanical response of the degrading polymer is determined experimentally using nano-dynamic mechanical analysis (nanoDMA). Water present in the polymer matrix contributes to hydrolysis and subsequent scission of polymer chains. Water in excess of hydrolysis, however, alters the load transfer mechanism within the polymer chains. Molecular mechanism study applied in this work provides detailed insights into the relative role of these two mechanisms, (i) chain scission and (ii) solvation, in the reduction of mechanical properties during degradation. Functional groups such as ester (-COO-) and terminal acid (-COOH) interact with water molecules leading to the formation of water bridges and solvation shells, respectively. These are found to hinder the load transfer between polymer chains. It is observed that, compared to scission, solvation plays a more active role in the reduction of mechanical properties of degrading PLA.

Solvent triggered irreversible shape morphism of biopolymer films.

Abstract: We report the controlled reversible and irreversible folding behavior of a biopolymer film simply by tuning the solvent characteristics. Generally, solvent triggered folding of soft membranes or film is achieved by unfolding. Here, we show that this unfolding behavior can be suppressed/delayed or even completely eliminated by altering the intrinsic nature of the solvent. A reversible folding of biopolymer film is observed in response to water, whereas, an irreversible folding is observed in the presence of an aromatic alcohol (AA) solution of different molar concentrations. The folding and unfolding behavior originates from the coupled deformation-diffusion phenomena. Our study indicates that the presence of an AA influences the relaxation behavior of polymer chains, which in turn affects the release of stored strain energy during folding. Controlling the reversibility as well as the actuation time of the biopolymer film by tuning the solvent is explained in detail at the bulk scale by applying appropriate experimental techniques. The underlying mechanism for the observed phenomena is complemented by performing a simulation study for a single polymer chain at the molecular length scale. Due to the solvent-triggered hygromorphic response, biopolymer films exhibit huge potential as sensors, soft robots, drug delivery agents, morphing medical devices and in biomedical applications. We provide experimental evidence for the weight lifting capacity of permanently folded membranes, amounting to ∼200 times their own weight.

Influence of Microstructure on the Nanomechanical Properties of Polymorphic Phases of Poly(vinylidene fluoride) B

Abstract: Poly(vinylidine fluoride) (PVDF) is a semicrystalline polymer which is known to exist in several polymorphic phases, namely, α, β, and γ. Each one of these polymorphic phases is characterized by unique features such as spherulite formation in the case of the α and γ phases and the presence of large piezoelectric and ferroelectric activity in the β phase. Despite being widely used as thin coatings in sensors, lack of reports on nanomechanical properties suggests that investigation of mechanical properties of PVDF, let alone those of its polymorphic phases, seems to have evaded the sight of the research community. Herein, we report the nanomechanical properties of the α, β, and γ phases of PVDF. The modulus and hardness values were evaluated from nanoindentation experiments; it was found that the electroactive β phase is the softest among the three polymorphic phases. This result was further confirmed by scratch experiments. We have attempted to establish a correlation between the microstructure and nanomechanical properties of these phases. This work sheds light on the mechanisms responsible for the observed mechanical behavior and the role of tie molecules and amorphous content in providing flexibility to the polymer.

Influence of Microstructure on the Nanomechanical Properties of Polymorphic Phases of Poly(vinylidene fluoride).

Abstract: Poly(vinylidine fluoride) (PVDF) is a semicrystalline polymer which is known to exist in several polymorphic phases, namely, α, β, and γ. Each one of these polymorphic phases is characterized by unique features such as spherulite formation in the case of the α and γ phases and the presence of large piezoelectric and ferroelectric activity in the β phase. Despite being widely used as thin coatings in sensors, lack of reports on nanomechanical properties suggests that investigation of mechanical properties of PVDF, let alone those of its polymorphic phases, seems to have evaded the sight of the research community. Herein, we report the nanomechanical properties of the α, β, and γ phases of PVDF. The modulus and hardness values were evaluated from nanoindentation experiments; it was found that the electroactive β phase is the softest among the three polymorphic phases. This result was further confirmed by scratch experiments. We have attempted to establish a correlation between the microstructure and nanomec...

Comparative Role of Chain Scission and Solvation in the Biodegradation of Polylactic Acid (PLA) B

Abstract: The molecular mechanism behind the process of biodegradation and consequently the loss in mechanical properties of polylactic acid (PLA) requires detailed understanding for the successful designing of various technological devices. In this study, we examine the role of free water and chain scission in this degradation process and quantify the mechanical properties of pristine and nanoparticle-reinforced PLA as it degrades over time. The in situ mechanical response of the degrading polymer is determined experimentally using nano-dynamic mechanical analysis (nanoDMA). Water present in the polymer matrix contributes to hydrolysis and subsequent scission of polymer chains. Water in excess of hydrolysis, however, alters the load transfer mechanism within the polymer chains. Molecular mechanism study applied in this work provides detailed insights into the relative role of these two mechanisms, (i) chain scission and (ii) solvation, in the reduction of mechanical properties during degradation. Functional groups such as ester (−COO−) and terminal acid (−COOH) interact with water molecules leading to the formation of water bridges and solvation shells, respectively. These are found to hinder the load transfer between polymer chains. It is observed that, compared to scission, solvation plays a more active role in the reduction of mechanical properties of degrading PLA.

Probing the Mechanical Response of Luminescent Dithiol-Protected Ag29(BDT)12(TPP)4 Cluster Crystals

Abstract: Atomically precise clusters of noble metals are considered to be an important class of advanced materials. Crystals of these clusters composed of inorganic cores and organic ligands are fascinating owing to their tunable and unique properties. Understanding their mechanical properties can give more insight into the design of nanocluster-based devices. Here, we probe the mechanical response of single crystals of Ag29(BDT)12(TPP)4 cluster (BDT = 1,3 benzenedithiol, TPP = triphenylphosphine) under both quasi-static and dynamic loading conditions. Surprisingly, the measured reduced Young’s modulus (Er) and hardness (H) were 4.48 and 0.285 GPa, respectively, similar to those of polymers and much smaller than the values for bulk silver. These observations indicate a significant role of capping ligands on the physical properties of such materials. The observed storage modulus, loss modulus and loss factor were also found to be similar to those of polymers. The magnitude of loss factor suggested the ability of nanocrystals to absorb energy under dynamic loading. These studies of mechanical properties of cluster materials could be useful in developing their applica-