Optimized process for the inclusion of carbon nanotubes in elastomers with improved thermal and mechanical properties

The effects of addition of reinforcing carbon nanotubes (CNTs) into hydrogenated nitrile-butadiene rubber (HNBR) matrix on the mechanical, dynamic viscoelastic, and permeability properties were studied in this investigation. Different techniques of incorporating nanotubes in HNBR were investigated in this research. The techniques considered were more suitable for industrial preparation of rubber composites. The nanotubes were modified with different surfactants and dispersion agents to improve the compatibility and adhesion of nanotubes on the HNBR matrix. The effects of the surface modification of the nanotubes on various properties were examined in detail. The amount of CNTs was varied from 2.5 to 10 phr in different formulations prepared to identify the optimum CNT levels. A detailed analysis was made to investigate the morphological structure and mechanical behavior at room temperature. The viscoelastic behavior of the nanotube filler elastomer was studied by dynamic mechanical thermal analysis (DMTA). Morphological analysis indicated a very good dispersion of the CNTs for a low nanotube loading of 3.5 phr. A significant improvement in the mechanical properties was observed with the addition of nanotubes. DMTA studies revealed an increase in the storage modulus and a reduction in the glass-transition temperature after the incorporation of the nanotubes. Further, the HNBR/CNT nanocomposites were subjected to permeability studies. The studies showed a significant reduction in the permeability of nitrogen gas. Copyright © 2011 Wiley Periodicals, Inc.

Delamination and wear in drilling of carbon-fiber reinforced plastic composites using multilayer TiAlN/TiN PVD-coated tungsten carbide tools

This study aims to investigate drilling process in carbon-fiber reinforced plastic (CFRP) composites with multilayer TiAlN/TiN PVD-coated tungsten carbide drill. The effect of process parameters have been investigated in drilling of Hexcel M21-T700GC. Thrust force and torque were measured online throughout the drilling experiments. Delamination were observed using optical microscope and analyzed via a developed algorithm based on digital image processing technique. Surface roughness of each hole was measured using a surface profilometer. In addition, the progression of tool wear in various surfaces of drill was observed using tool microscope and measured using image software. Our results indicate that the thrust force and torque increased with the increasing cutting speed and feed rate. Delamination and average surface roughness that rose with the increase in feed rate, however, decreased with the increasing cutting speed. The average surface roughness tended to increase with the increase in feed rate and decrease with the increasing cutting speed in drilling of carbon-fiber reinforced plastic (CFRP). Feed rate was found as the predominant factor on the drilling outputs. Abrasive wear was observed on both flank and relief surfaces, which created edge wear on cutting edges. No sign of chipping or plastic deformation has been observed on the surfaces of drills. © 2012 The Author(s).

Stiffness analysis of polymeric composites using the finite element method

The ability to predict the mechanical behavior of polymer composites is crucial for their design and manufacture. Extensive studies based on both macro- and micromechanical analyses are used to develop new insights into the behavior of composites. In this respect, finite element modeling has proved to be a particularly powerful tool. In this article, we present a Galerkin scheme in conjunction with the penalty method for elasticity analyses of different types of polymer composites. In this scheme, the application of Green's theorem to the model equation results in the appearance of interfacial flux terms along the boundary between the filler and polymer matrix. It is shown that for some types of composites these terms significantly affect the stress transfer between polymer and fillers. Thus, inclusion of these terms in the working equations of the scheme preserves the accuracy of the model predictions. The model is used to predict the most important bulk property of different types of composites. Composites filled with rigid or soft particles, and composites reinforced with short or continuous fibers are investigated. For each case, the results are compared with the available experimental results and data obtained from other models reported in the literature. Effects of assumptions made in the development of the model and the selection of the prescribed boundary conditions are discussed.

Prediction of failure and fracture mechanisms of polymeric composites using finite element analysis. Part 2:Fiber reinforced composites

A robust finite element scheme for the micro-mechanical modeling of the behavior of fiber reinforced polymeric composites under external loads is developed. The developed model is used to simulate stress distribution throughout the composite domain and to identify the locations where maximum stress concentrations occur. This information is used as a guide to predict dominant failure and crack growth mechanisms in fiber reinforced composites. The differences between continuous fibers, which are susceptible to unidirectional transverse fracture, and short fibers have been demonstrated. To assess the validity and range of applicability of the developed scheme, numerical results obtained by the model are compared with the available experimental data and also with the values found using other methods reported in the literature. These comparisons show that the present finite element scheme can generate meaningful results in the analysis of fiber reinforced composites.

Hard coatings on elastomers for reduced permeability and increased wear resistance

In this study, three different elastomers, namely hydrogenated nitrile butadiene rubber, fluoroelastomer and silicone, have been subjected to two different hard metallised coatings by ion implantation process. The three different elastomers are commonly used in various seal applications, where reduced wear and gas permeability are essential in maintaining seal performance and functionality. Samples of these rubbers have been coated with chromium coating in one set of tests. In the second set of tests, samples of elastomers have been coated with tungsten carbide coating being deposited on all the three different elastomers. Wear, gas permeability and mechanical behaviour of the coated samples were compared with each other and with the control uncoated elastomers. All the coated samples showed good reduction in gas permeability. With the use of metallised coatings, there has been improved resistance to wear in all the coated samples. Adhesion strength and effect of coating on the elastomer have been investigated by mechanical testing. Mechanical tests revealed good adhesion of metal coatings on all the rubber samples, and there was no detrimental effect on the mechanical properties after coating. © 2012 Institute of Materials, Minerals and Mining.

Modified Silicone Elastomer Vaginal Gels for Sustained Release of Antiretroviral HIV Microbicides

We previously reported nonaqueous silicone elastomer gels (SEGs) for sustained vaginal administration of the CCR5-targeted entry inhibitor maraviroc (MVC). Here, we describe chemically modified SEGs (h-SEGs) in which the hydrophobic cyclomethicone component was partially replaced with relatively hydrophilic silanol-terminated polydimethylsiloxanes (st-PDMS). MVC and emtricitabine (a nucleoside reverse transcriptase inhibitor), both currently under evaluation as topical microbicides to counter sexual transmission of human immunodeficiency virus type 1 (HIV-1), were used as model antiretroviral (ARV) drugs. Gel viscosity and in vitro ARV release were significantly influenced by st-PDMS molecular weight and concentration in the h-SEGs. Unexpectedly, gels prepared with lower molecular weight grades of st-PDMS showed higher viscosities. h-SEGs provided enhanced release over 24 h compared with aqueous hydroxyethylcellulose (HEC) gels, did not modify the pH of simulated vaginal fluid (SVF), and were shown to less cytotoxic than standard HEC vaginal gel. ARV solubility increased as st-PDMS molecular weight decreased (i.e., as percentage hydroxyl content increased), helping to explain the in vitro release trends. Dye ingression and SVF dilution studies confirmed the increased hydrophilicity of the h-SEGs. h-SEGs have potential for use in vaginal drug delivery, particularly for ARV-based HIV-1 microbicides.

Multilayered glass fibre-reinforced composites in rotational moulding

The potential of multiple layer fibre-reinforced mouldings is of growing interest to the rotational moulding industry because of their cost/performance ratio. The particular problem that arises when using reinforcements in this process relate to the fact that the process is low shear and good mixing of resin and reinforcement is not optimum under those conditions. There is also a problem of the larger/heavier reinforcing agents segregating out of the powder to lay up on the inner part surface. In this study, short glass fibres were incorporated and distributed into a polymer matrix to produce fibre-reinforced polymer composites using the rotational moulding process and characterised in terms of morphology and mechanical properties. © 2011 American Institute of Physics.

Mechanical properties of polyamide 6 reinforced microfibrilar composites

The mechanical behavior of microfibrilar composites (MFC), consisting of a matrix of high-density polyethylene (HDPE) and reinforcement of polyamide 6 (PA6) fibrils, with and without compatibilization, was studied. The composites were produced by conventional processing techniques with various shape and arrangement of the PA6 reinforcing entities: long, unidirectional, or crossed bundles of fibrils (UDP and CPC, respectively), middle-length, randomly oriented bristles (MRB), or non-oriented micrometric PA6 spheres (NOM). The tensile, flexural, and impact properties of the MFC materials (UDP, CPC, and MRB) were determined as a function of the PA6 reinforcement shape, alignment and content, and compared with those of NOM, the non-fibrous composite. It was concluded that the in-situ MFC materials based on HDPE/PA6 blends display improvements in the mechanical behavior when compared with the neat HDPE matrix, e.g., up to 33% for the Young modulus, up to 119% for the ultimate tensile strength, and up to 80% for the flexural stiffness. Copyright © 2011 Society of Plastics Engineers.

Evaluation of the Factors Contributing to Levonorgestrel Binding in Addition Cure Silicone Elastomer Vaginal Rings

Background: Following progress of the dapivirine (DPV)-releasing silicone elastomer (SE) vaginal ring (VR) into Phase III clinical studies, there is now interest in developing next-generation rings that additionally provide contraception. Levonorgestrel (LNG) is a safe and effective progestin that is being widely considered for use as a hormonal contraceptive agent in future multipurpose prevention technology (MPT) products. Although LNG has previously been incorporated into various controlled release SE devices, minimal attention has focused on its propensity to irreversibly react with addition cure SE systems. Here, for the first time, we investigate this LNG binding phenomenon and outline strategies for overcoming it.
Methods: VRs containing various loadings of DPV and LNG were manufactured and in vitro release assessed. Different LNG-only SE samples were also prepared to assess the following parameters: (i) addition cure vs. condensation cure SEs; (ii) different types of addition cure SEs; (iii) mixing time, (iv) cure temperature, (v) cure time; and (vi) LNG particle size. After manufacture, the LNG-only samples were assayed for total drug content using a solvent extraction method. The SE curing reaction and the LNG binding reaction was probed using nuclear magnetic resonance (NMR) spectroscopy. Results:
Under certain drug/formulation/processing conditions, LNG was not recoverable from VRs. Further studies using non-ring samples showed that: (a) the phenomenon was only observed with addition cure SEs (and not condensation cure SEs); (b) the extent of binding was dependent upon the type of addition cure SE; (c) micronised LNG showed significantly greater binding than non-micronised LNG; (d) the extent of binding correlated with increased mixing time, cure time and cure temperature.
Conclusions: Careful control of the API characteristics, the SE composition, and the manufacturing conditions will be necessary to establish a practical VR formulation for controlled release of LNG.

Development of Novel Post-Tensioned Glulam Timber Composites

Improvements in the structural performance of glulam timber beams by the inclusion of reinforcing materials can increase both the service performance and ultimate capacity. In recent years research focusing on the addition of fibre reinforced polymers (FRP) to strengthen members has yielded positive results. However, the FRP material is still relatively expensive and its full potential in combination with structural timber has not been realised. This paper describes a series of four-point bending tests that were conducted, under service loads and to failure, on unreinforced, reinforced and post-tensioned glulam timber beams, where the reinforcing tendon used was 12mm diameter basalt fibre reinforced polymer (BFRP). The research was designed to evaluate the benefits offered by including an active reinforcement in contrast to the passive reinforcement typically used within timber strengthening works, in addition to establishing the affect that bonding the reinforcing tendon has on the material’s performance. Further experimental tests have been developed to investigate the long-term implications of this research, with emphasis placed upon creep and loss of post-tensioning.
The laboratory investigations established that the flexural strength and stiffness increased for both the unbonded and bonded post-tensioned timbers compared to the unreinforced beams. Timber that was post-tensioned with an unbonded BFRP tendon showed a flexural strength increase of 2.8% and an increase in stiffness of 8.7%. Post-tensioned beams with a bonded BFRP tendon showed increases in flexural strength and stiffness of 16.6% and 11.5% respectively.

Effects of particle/matrix interface and strengthening mechanisms on the mechanical properties of metal matrix composites

A randomly distributed multi-particle model considering the effects of particle/matrix interface and strengthening mechanisms introduced by the particles has been constructed. Particle shape, distribution, volume fraction and the particles/matrix interface due to the factors including element diffusion were considered in the model. The effects of strengthening mechanisms, caused by the introduction of particles on the mechanical properties of the composites, including grain refinement strengthening, dislocation strengthening and Orowan strengthening, are incorporated. In the model, the particles are assumed to have spheroidal shape, with uniform distribution of the centre, long axis length and inclination angle. The axis ratio follows a right half-normal distribution. Using Monte Carlo method, the location and shape parameters of the spheroids are randomly selected. The particle volume fraction is calculated using the area ratio of the spheroids. Then, the effects of particle/matrix interface and strengthening mechanism on the distribution of Mises stress and equivalent strain and the flow behaviour for the composites are discussed.

Preparation and surface modification of submicron YAl2 particles by mixed milling with magnesium for fabricating YAl2p/MgLiAl composites

A new process for the preparation and surface modification of submicron YAl2 intermetallic particles was proposed to control the agglomeration of ultrafine YAl2 particles and interface in the fabrication of YAl2p/MgLiAl composites. The morphological and structural evolution during mechanical milling of YAl2 powders (< 30 μm) with magnesium particles (~ 100 μm) has been characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The results show that YAl2 particles are refined to submicron scale and separately cladded in magnesium coatings after mixed milling with magnesium particles for 20 h. Mechanical and metallurgical bonds have been found in YAl2/Mg interfaces without any interface reactions. Both the refining and mechanical activation efficiencies for YAl2 particles are enhanced, which may be related to the addition of magnesium particles leading to atomic solid solution and playing a role as “dispersion stabilizer”.

Electrical conduction and rheological behaviour of composites of poly(epsilon-caprolactone) and MWCNTs

Two mechanisms of conduction were identified from temperature dependent (120 K-340 K) DC electrical resistivity measurements of composites of poly(c-caprolactone) (PCL) and multi-walled carbon nanotubes (MWCNTs). Activation of variable range hopping (VRH) occurred at lower temperatures than that for temperature fluctuation induced tunneling (TFIT). Experimental data was in good agreement with the VRH model in contrast to the TFIT model, where broadening of tunnel junctions and increasing electrical resistivity at T > T-g is a consequence of a large difference in the coefficients of thermal expansion of PCL and MWCNTs. A numerical model was developed to explain this behavior accounting for a thermal expansion effect by supposing the large increase in electrical resistivity corresponds to the larger relative deformation due to thermal expansion associated with disintegration of the conductive MWCNT network. MWCNTs had a significant nucleating effect on PCL resulting in increased PCL crystallinity and an electrically insulating layer between MWCNTs. The onset of rheological percolation at similar to 0.18 vol% MWCNTs was clearly evident as storage modulus, G' and complex viscosity, vertical bar eta*vertical bar increased by several orders of magnitude. From Cole-Cole and Van Gurp-Palmen plots, and extraction of crossover points (G(c)) from overlaying plots of G' and G '' as a function of frequency, the onset of rheological percolation at 0.18 vol% MWCNTs was confirmed, a similar MWCNT loading to that determined for electrical percolation. 

Melt Processing and Properties of Polyamide 6/Graphene Nanoplatelet Composites

Graphene, due to its outstanding properties, has become the topic of much research activity in recent years. Much of that work has been on a laboratory scale however, if we are to introduce graphene into real product applications it is necessary to examine how the material behaves under industrial processing conditions. In this paper the melt processing of polyamide 6/graphene nanoplatelet composites via twin screw extrusion is investigated and structure–property relationships are examined for mechanical and electrical properties. Graphene nanoplatelets (GNPs) with two aspect ratios (700 and 1000) were used in order to examine the influence of particle dimensions on composite properties. It was found that the introduction of GNPs had a nucleating effect on polyamide 6 (PA6) crystallization and substantially increased crystallinity by up to 120% for a 20% loading in PA6. A small increase in crystallinity was observed when extruder screw speed increased from 50 rpm to 200 rpm which could be attributed to better dispersion and more nucleation sites for crystallization. A maximum enhancement of 412% in Young's modulus was achieved at 20 wt% loading of GNPs. This is the highest reported enhancement in modulus achieved to date for a melt mixed thermoplastic/GNPs composite. A further result of importance here is that the modulus continued to increase as the loading of GNPs increased even at 20 wt% loading and results are in excellent agreement with theoretical predictions for modulus enhancement. Electrical percolation was achieved between 10–15 wt% loading for both aspect ratios of GNPs with an increase in conductivity of approximately 6 orders of magnitude compared to the unfilled PA6.