During the resorbable-polymer-boom of the 1970s and 1980s, polycaprolactone (PCL) was used in the biomaterials field and a number of drug-delivery devices. Its popularity was soon superseded by faster resorbable polymers which had fewer perceived disadvantages associated with long term degradation (up to 3-4 years) and intracellular resorption pathways; consequently, PCL was almost forgotten for most of two decades. Recently, a resurgence of interest has propelled PCL back into the biomaterials-arena. The superior rheological and viscoelastic properties over many of its aliphatic polyester counterparts renders PCL easy to manufacture and manipulate into a large range of implants and devices. Coupled with relatively inexpensive production routes and FDA approval, this provides a promising platform for the production of longer-term degradable implants which may be manipulated physically, chemically and biologically to possess tailorable degradation kinetics to suit a specific anatomical site. This review will discuss the application of PCL as a biomaterial over the last two decades focusing on the advantages which have propagated its return into the spotlight with a particular focus on medical devices, drug delivery and tissue engineering.

The return of a forgotten polymer : Polycaprolactone in the 21st century

Nanoparticles can influence the properties of polymer materials by a variety of mechanisms. With fullerene, carbon nanotube, and clay or graphene sheet nanocom- posites in mind, we investigate how particle shape influences the melt shear viscosity ! and the tensile strength " , which we determine via molecular dynamics simula- tions. Our simulations of compact (icosahedral), tube or rod-like, and sheet-like model nanoparticles, all at a volume fraction # ! 0.05, indicate an order of magnitude increase in the viscosity ! relative to the pure melt. This finding evidently can not be explained by continuum hydrodynamics and we provide evidence that the ! increase in our model nanocomposites has its origin in chain bridging between the nanopar- ticles. We find that this increase is the largest for the rod-like nanoparticles and least for the sheet-like nanoparticles. Curiously, the enhancements of ! and " exhibit opposite trends with increasing chain length N and with particle shape anisotropy. Evidently, the concept of bridging chains alone cannot account for the increase in " and we suggest that the deformability or flexibility of the sheet nanoparticles con- tributes to nanocomposite strength and toughness by reducing the relative value of the Poisson ratio of the composite. The molecular dynamics simulations in the present work focus on the reference case where the modification of the melt structure associ- ated with glass-formation and entanglement interactions should not be an issue. Since many applications require good particle dispersion, we also focus on the case where the polymer-particle interactions favor nanoparticle dispersion. Our simulations point to a substantial contribution of nanoparticle shape to both mechanical and processing prop- erties of polymer nanocomposites. © 2007 Wiley Periodicals, Inc." J Polym Sci Part B: Polym

http://absimage.aps.org/image/MAR07/MWS_MAR07-2006-002162.pdf

The Effect of Nanoparticle Shape on Polymer-Nanocomposite Rheology and Tensile Strength

In the present study, the two grafting techniques grafting-from - by activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) - and grafting-to - by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) - were systematically compared, employing cellulose as a substrate. In order to obtain a meaningful comparison, it is crucial that the graft lengths of the polymers that are grafted from and to the substrates are essentially identical. Herein, this was achieved by utilizing the free polymer formed in parallel to the grafting-from reaction as the polymer for the grafting-to reaction. Four graft lengths were investigated, and the molar masses of the four free polymers (21 ≤ Mn ≤ 100 kDa; 1.07 ≤ M ≤ 1.26), i.e. the polymers subsequently employed in the grafting-to reaction, were shown to be in the same range as the molar masses of the polymers grafted from the surface (23 ≤ Mn ≤ 87 kDa; 1.08 ≤ M ≤ 1.31). The molecular weights of the chains grafted from the surface were established after cleavage from the cellulose substrates via size exclusion chromatography (SEC). High-resolution Fourier transform infrared microscopy (FT-IRM) was employed as an efficient tool to study the spatial distribution of the polymer content on the grafted substrates. In addition, the functionalized substrates were analyzed by X-ray photoelectron spectroscopy (XPS), contact angle (CA) measurements, and field-emission scanning electron microscopy (FE-SEM). For cellulose substrates modified via the grafting-from approach, the content of polymer on the surfaces increased with increasing graft length, confirming the possibility to tailor not only the length of the polymer grafts but also the polymeric content on the surface. In comparison, for the grafting-to reaction, the grafted content could not be controlled by varying the length of the preformed polymer: the polymer content was essentially the same for the four graft lengths. Consequently, the obtained results, when employing cellulose as a substrate and under these conditions, suggest that the grafting-from approach is superior to the grafting-to technique with respect to controlling the distribution of the polymeric content on the surface. © 2012 American Chemical Society.

Grafting efficiency of synthetic polymers onto biomaterials: A comparative study of grafting- from versus grafting- to

The aim of the present research work is to enhance the thermal and dynamic mechanical properties of Kevlar/Cocos nucifera sheath (CS)/epoxy composites with graphene nano platelets (GNP). Laminates were fabricated through the hand lay-up method followed by hot pressing. GNP at different wt.% (0.25, 0.5, and 0.75) were incorporated with epoxy resin through ultra-sonication. Kevlar/CS composites with different weight ratios (100/0, 75/25, 50/50, 25/75, 0/100) were fabricated while maintaining a fiber/matrix weight ratio at 45/55. Thermal degradation and viscoelastic properties were evaluated using thermogravimetric analysys (TGA), differential scanning calorimetric (DSC) analysis, and a dynamic mechanical analyser (DMA). The obtained results revealed that Kevlar/CS (25/75) hybrid composites at 0.75 wt.% of GNP exhibited similar thermal stability compared to Kevlar/epoxy (100/0) composites at 0 wt.% of GNP. It has been corroborated with DSC observation that GNP act as a thermal barrier. However, DMA results showed that the Kevlar/CS (50/50) hybrid composites at 0.75 wt.% of GNP exhibited almost equal viscoelastic properties compared to Kevlar/epoxy (100/0) composites at 0 wt.% GNP due to effective crosslinking, which improves the stress transfer rate. Hence, this research proved that Kevlar can be efficiently (50%) replaced with CS at an optimal GNP loading for structural applications.

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Enhanced Thermal and Dynamic Mechanical Properties of Synthetic/Natural Hybrid Composites with Graphene Nanoplateletes

Carbonyl iron powders as absorption material for microwave interference shielding: A review

The thermal degradation and dynamic mechanical properties modeling of MWCNT/glass fiber multiscale filler reinforced polypropylene composites

High performance epoxy composites are now a days a must in several industrial applications. In the present work electrospun polyimide (PI) nanofibers with excellent thermal and mechanical properties was used as a reinforcement in epoxy matrix via a simple mechanical mixing followed by thermal curing method. Well defined electrospun nanofibers of aromatic polyimide (PI) were successfully prepared from electrospinning Poly (amic acid) (PAA) and subsequent thermal treatment. The fiber morphology was analyzed using Transmission electron microscopy (TEM) and Atomic force microscopy (AFM). PI/epoxy nanocomposites with different PI loadings were prepared using chopped PI mats. The dynamic mechanical performance of these PI/epoxy composites was investigated to determine the influence of PI fibers in reinforcing the epoxy matrix. The fracture toughness of these composites displayed a note worthy improvement of 20 % at 1 w% loaded samples and the surface of the fractured samples was investigated by Scanning electron microscope. The rheological properties of these systems show a tremendous increase in the storage and loss modulus when compared to neat systems. In addition flow models were employed to model the rheological data and the comparison was made with the experimental data.

B.D.S. Deeraj

Papers

The thermal degradation and dynamic mechanical properties modeling of MWCNT/glass fiber multiscale filler reinforced polypropylene composites

Enhanced visco-elastic and rheological behavior of epoxy composites reinforced with polyimide nanofiber

Triblock copolymer grafted Graphene oxide as nanofiller for toughening of epoxy resin

Graphene Oxide as a Prospective Graft in Polyethylene Glycol for Enhancing the Toughness of Epoxy Nanocomposites

Graphene oxide as multi-functional initiator and effective molecular reinforcement in PVP/epoxy composites