Radiopacity and Chemical resistance of Elastomer-Barium sulphate nanocomposites

The Human race of our century is in gluttonous search for novel engineering products which led to a skyrocketed progress in research and fabrication of filled polymers. Recently, a big window has been opened up for speciality polymers especially elastomers with promising properties. Among the many reasons why rubbers are widely used in the process industries, three are considered as important. Firstly, rubbers operate in a variety of environments and possess usable ranges of deformity and durability and can be exploited through suitable and more or less conventional equipment design principles. Secondly, rubber is an eminently suitable construction material for protection against corrosion in the chemical plant and equipment against various corrosive chemicals as, acids and alkalies and if property tailored, can shield ionising radiations as X-rays and gamma rays in medical industry, with minimum maintenance lower down time, negligible corrosion and a preferred choice for aggressive corroding and ionising environment. Thirdly, rubber can readily and hastily, and at a relatively lower cost, be converted into serviceable products, having intricate shapes and dimensions. In a century’s gap, large employment of flexible polymer materials in the different segments of industry has stimulated the development of new materials with special properties, which paved its way to the synthesis of various nanoscale materials. At nano scale, one makes an entry into a world where multidisciplinary sciences meet and utilises the previously unapproached infinitesimal length scale, having dimension which measure upto one billionth of a meter, to create novel properties. The nano fillers augment the elastomers properties in an astonishing fashion due to their multifunctional nature and unprecedented properties have been exhibited by these polymer-nanocomposites just to beat the shortcomings of traditional micro composites. The current research aims to investigate the possibility of using synthesised nano barium sulphate for fabricating elastomer-based nanocomposites and thereby imparting several properties to the rubber. In this thesis, nano materials, their synthesis, structure, properties and applications are studied. The properties of barium sulphate like chemical resistance and radiopacity have been utilized in the present study and is imparted to the elastomers by preparing composites.

Hybrid layer-by-layer assembly based on animal and vegetable structural materials: multilayered films of collagen and cellulose nanowhiskers

Layer-by-layer (LBL) assembly was used to combine crystalline rod-like nanoparticles obtained from a vegetable source, cellulose nanowhiskers (CNWs), with collagen, the main component of skin and connective tissue found exclusively in animals. The film growth of the multilayered collagen/CNW was monitored by UV-Vis spectroscopy and ellipsometry measurements, whereas the film morphology and surface roughness were characterized by SEM and AFM. UV-Vis spectra showed the deposition of the same amount of collagen, 5 mg m(-2), in each dipping cycle. Ellipsometry data showed an increment in thickness with the number of layers, and the average thickness of each bilayer was found to be 8.6 nm. The multilayered bio-based nanocomposites were formed by single layers of densely packed CNWs adsorbed on top of each thin collagen layer where the hydrogen bonding between collagen amide groups and OH groups of the CNWs plays a mandatory role in the build-up of the thin films. The approach used in this work represents a potential strategy to mimic the characteristics of natural extracellular matrix (ECM) which can be used for applications in the biomedical field.

Interfacial interactions and structure of organic-inorganic nanohybrids

Understanding the interfacial interactions and structure is important to better design and application of organic-inorganic nanohybrids. This paper presents our recent molecular dynamic studies on organoclays and polymer nanocomposites, including the layering behavior of organoclays, structural and dynamic properties of dioctadecyldimethyl ammoniums in organoclays, and interfacial interactions and structure of polyurethane nanocomposites. The results demonstrate that the layering behaviors of organoclays are closely related to the chain length of quaternary alkyl ammoniums and cation exchangeable capacity of clays. In addition to typical layered structures such as monolayer, bilayer and pseudo-trilayer, a pseudo-quadrilayer structure was also observed in organoclays modified with dioctadecyldimethyl ammoniums (DODDMA). In such a structure, alkyl chains do not lie flat within a single layer but interlace, and also jump to the next layer or even the next nearest layer. Moreover, the diffusion constants of nitrogen and methylene atoms increase with the temperature and methelene towards the tail groups. For polyurethane nanocomposite, the van der Waals interaction between apolar alkyl chains and soft segments of polyurethane predominates the interactions between organoclay and polyurethane. Different from most bulk polyurethane systems, there is no distinct phase-separated structure for the polyurethane.

Carbon Nanofiber Type and Content Dependence of the Physical Properties of Carbon Nanofiber Reinforced Polypropylene Composites

The variation of the physical properties of four differ- ent carbon nanofibers (CNFs), based-polymer nano- composites incorporated in the same polypropylene (PP) matrix by twin-screw extrusion process was investigated. Nanocomposites fabricated with CNFs with highly graphitic outer layer revealed electrical isolation-to-conducting behaviors as function of CNF’s content. Nanocomposites fabricated with CNFs with an outer layer consisting on a disordered pyro- litically stripped layer, in contrast, revealed better mechanical performance and enhanced thermal sta- bility. Further, CNF’s incorporation into the polymer increased the thermal stability and the degree of crystallinity of the polymer, independently on the filler content and type. In addition, dispersion of the CNFs’ clusters in PP was analyzed by transmitted light opti- cal microscopy, and grayscale analysis (GSA). The results showed a correlation between the filler concentration and the variance, a parameter which measures quantitatively the dispersion, for all composites. This method indicated a value of 1.4 vol% above which large clusters of CNFs cannot be dispersed effectively and as a consequence only slight changes in mechanical performance are observed. Finally, this study establishes that for tailoring the physical properties of CNF based-polymer nanocomposites, both adequate CNFs structure and content have to be chosen.

Preparação de suspensões aquosas de nanopartículas de carbono para deposição em superfícies

Dissertação de mestrado integrado em Engenharia de Materiais

Nanocompósitos de matriz polimérica: estratégias de síntese de materiais híbridos

Associating the well known advantages of hybrid materials to the wide potential of nanomaterials, the new and featuring class of polymer nanocomposites turned into one of the most intensively researched areas. This review highlights recent developments in the field of the synthesis of polymer based nanocomposites. Important issues related to the surface modification of fillers, in order to promote the compatibility between the inorganic/organic components, are also reported. The enhancement of the physical properties and the potential applications of polymer nanocomposites are considered in typical examples, given for each synthetic method described.

Modification of Polypropylene and Polystyrene Using Nanosilica

The present work focuses on the modification of the commonly used thermoplastics, polypropylene and polystyrene using nanosilica preparcd from a cheap source of sodium silicate. Melt compounding technique has been used for nanocomposite preparation as it is simple and suited to injection moulding. Nanosilica in a polymer matrix provide significant enhancement in strength, stiffness and impact strength. Incorporation of silica particles in a polymer also improves its thennal stability. To achieve better dispersion of fillers in polymer matrices the mixing was done at different shear rates. The enhancement in material properties indicates that at higher shear rates there is greater interaction between particles and the matrix and it depends on filler concentration and type of polymer used. N anosilica is a useful filler in thennoplastic polymers and has been applied in automotive applications, electronic appliances and consumer goods.This thesis is divided into six chapters. General introduction to the topic is described in chapter 1. Salient features of polymer nanocomposites, their synthesis, properties and applications are presented. A review of relevant literature and the scope and objectives are also mentioned in this chapter.The materials used and the vanous experimental method and techniques employed in the study are described in chapter 2. Preparation of nanocomposites by melt blending using Thenno Haake Rheocord, preparation of samples, evaluation of mechanical and thennal properties using UTM, Impact testing and characterization using DMA, TGA and DSC and morphology by SEM are described.The preparation of nanosilica from a laboratory scale to a pilot plant scale is described in chapter 3. Generation of surface modified silica, evaluation of kinetic parameters of the synthesis reaction, scale up of the reactor and modeling of the reactor are also dealt with in this chapter.The modification of the commodity thennoplastic, Polypropylene using nanosilica is described in chapter 4. Preparation of PP/silica nanocomposites, evaluation of mechanical properties, thermal and crystallization characteristics, water absorption and ageing resistance studies are also presented.The modification of Polystyrene using synthesized nanosilica IS described in chapter 5. The method of preparation of PS/silica nanocomposites, evaluation of mechanical properties (static and dynamic), thermal properties melt flow characteristics using Haake Rheocord, water absorption and ageing resistance of these nanocomposites are studied.

Studies on the use of Nanokaolin, MWCNT and Graphene in NBR and SBR

The current research investigates the possibility of using unmodified and modified nanokaolin, multiwalled carbon nanotube (MWCNT) and graphene as fillers to impart enhancement in mechanical, thermal, and electrical properties to the elastomers. Taking advantage of latex blending method, nanoclay, MWCNT and graphene dispersions, prepared by ultra sound sonication are dispersed in polymer latices. The improvement in material properties indicated better interaction between filler and the polymer.MWCNT and graphene imparted electrical conductivity with simultaneous improvement in mechanical properties. Layered silicates prepared by microwave method also significantly improve the mechanical properties of the nanocomposites. The thesis entitled ‘Studies on the use of Nanokaolin, MWCNT and Graphene in NBR and SBR’ consists of ten chapters. The first chapter is a concise introduction of nanocomposites, nanofillers, elastomeric matrices and applications of polymer nanocomposites. The state-of-art research in elastomer based nanocomposites is also presented. At the end of this chapter the main objectives of the work are mentioned. Chapter 2 outlines the specifications of various materials used, details of experimental techniques employed for preparing and characterizing nanocomposites. Chapter3 includes characterization of the nanofillers, optimsation of cure time of latex based composites and the methods used for the preparation of latex based and dry rubber based nanocomposites. Chapter4 presents the reinforcing effect of the nanofillers in XNBR latex and the characterization of the nanocomposites. Chapter5 comprises the effect of nanofillers on the properties of SBR latex and their characterization Chapter 6 deals with the study of cure characteristics, mechanical and thermal properties and the characterization of NBR based nanocomposites. Chapter7 is the microwave studies of MWCNT and graphene filled elastomeric nanocomposites. Chapter 8 gives details of the preparation of layered silicates, their characterization and use in different elastomeric matrices. Chapter 9 is the study of mechanical properties of nanoclay incorporated nitrile gloves .Chapter 10 presents the summary and conclusions of the investigation.

Modification of Polypropylene/High Density Polyethylene Blend Using Nanokaolinite Clay and E-Glass Fibre: Preparation, Characterization and Micromechanical Modelling

Upgrading two widely used standard plastics, polypropylene (PP) and high density polyethylene (HDPE), and generating a variety of useful engineering materials based on these blends have been the main objective of this study. Upgradation was effected by using nanomodifiers and/or fibrous modifiers. PP and HDPE were selected for modification due to their attractive inherent properties and wide spectrum of use. Blending is the engineered method of producing new materials with tailor made properties. It has the advantages of both the materials. PP has high tensile and flexural strength and the HDPE acts as an impact modifier in the resultant blend. Hence an optimized blend of PP and HDPE was selected as the matrix material for upgradation. Nanokaolinite clay and E-glass fibre were chosen for modifying PP/HDPE blend. As the first stage of the work, the mechanical, thermal, morphological, rheological, dynamic mechanical and crystallization characteristics of the polymer nanocomposites prepared with PP/HDPE blend and different surface modified nanokaolinite clay were analyzed. As the second stage of the work, the effect of simultaneous inclusion of nanokaolinite clay (both N100A and N100) and short glass fibres are investigated. The presence of nanofiller has increased the properties of hybrid composites to a greater extent than micro composites. As the last stage, micromechanical modeling of both nano and hybrid A composite is carried out to analyze the behavior of the composite under load bearing conditions. These theoretical analyses indicate that the polymer-nanoclay interfacial characteristics partially converge to a state of perfect interfacial bonding (Takayanagi model) with an iso-stress (Reuss IROM) response. In the case of hybrid composites the experimental data follows the trend of Halpin-Tsai model. This implies that matrix and filler experience varying amount of strain and interfacial adhesion between filler and matrix and also between the two fillers which play a vital role in determining the modulus of the hybrid composites.A significant observation from this study is that the requirement of higher fibre loading for efficient reinforcement of polymers can be substantially reduced by the presence of nanofiller together with much lower fibre content in the composite. Hybrid composites with both nanokaolinite clay and micron sized E-glass fibre as reinforcements in PP/HDPE matrix will generate a novel class of high performance, cost effective engineering material.

Desenvolvimento e caracterização de nanocompósito de resina epóxi com nanopartículas de sílica para revestimento de dutos para transporte de petróleo

The use of polymer based coatings is a promising approach to reduce the corrosion problem in carbon steel pipes used for the transport of oil and gas in the oil industry. However, conventional polymer coatings offer limited properties, which often cannot meet design requirements for this type of application, particularly in regard to use temperature and wear resistance. Polymer nanocomposites are known to exhibit superior properties and, therefore, offer great potential for this type of application. Nevertheless, the degree of enhancement of a particular property is greatly dependent upon the matrix/nanoparticle material system used, the matrix/nanoparticle interfacial bonding and also the state of dispersion of the nanoparticle in the polymer matrix. The objective of the present research is to develop and characterize polymer based nanocomposites to be used as coatings in metallic pipelines for the transportation of oil and natural gas. Epoxy/SiO2 nanocomposites with nanoparticle contents of 2, 4, and 8 wt % were processed using a high-energy mill. Modifications of the SiO2 nanoparticles‟ surfaces with two different silane agents were carried out and their effect on the material properties were investigated. The state of dispersion of the materials processed was studied using Scanning and Transmission Electron Microscopy (SEM and TEM) micrographs. Thermogravimetric analysis (TG) were also conducted to determine the thermal stability of the nanocomposites. In addition, the processed nanocomposites were characterized by dynamic mechanical analysis (DMA) to investigate the effect of nanoparticles content and silane treatment on the viscoelastic properties and on the glass transition temperature. Finally, wear tests of the pin-on-disc type were carried out to determine the effects of the nanoparticles and the silane treatments studied. According to the results, the addition of SiO2 nanoparticles treated with silane increased the thermal stability, the storage modulus and Tg of the epoxy resin and decreased wear rate. This confirms that the interaction between the nanoparticles and the polymer chains plays a critical role on the properties of the nanocomposites

Percolated non-Newtonian flow for silicone obtained from exfoliated bioinorganic layered double hydroxide intercalated with amino acid

A simple and scalable procedure was used to obtain thin, stable, homogeneous, and easy-to-handle films composed of silicone derived from dimethicones containing dispersed hydrotalcite-type materials previously organo-modified with amino acids. The absence of the typical X-ray pattern of the bioinorganic LDH filler suggested an exfoliation process that was further indirectly evidenced by a drastic change in the rheological behavior, which turned from a quasi-Newtonian behavior for the silicone free of LDH filler to an extensive developed gel-like structure for the nanocomposite derivatives. Visualized by the shear-thinning exponent of the complex viscosity in the low-frequency range, the percolation threshold was evident for filler loading as low as <5 w/W%, suggesting the presence of a largely developed interface between the filler and the polymer. The increase of more than one order of magnitude in viscosity was explained by the rather strong attrition phenomenon between the tethered amino acid anions and the silicone chains. UVB radiation absorption profiles make such bioinorganic polymer nanocomposites potentially applicable in skin protection. Thermo-gravimetric analysis revealed significant improvement in the thermal stability, especially in the final step of the polymer combustion, thus underlining the role of the hybrid material as a thermal retardant agent. (C) 2011 Elsevier B.V. All rights reserved.

Cellulose micro/nanofibres from Eucalyptus kraft pulp: Preparation and properties

There is growing interest in cellulose nanofibres from renewable sources for several industrial applications. However, there is a lack of information about one of the most abundant cellulose pulps: bleached Eucalyptus kraft pulp. The objective of the present work was to obtain Eucalyptus cellulose micro/nanofibres by three different processes, namely: refining, sonication and acid hydrolysis of the cellulose pulp. The refining was limited by the low efficiency of isolated nanofibrils, while sonication was more effective for this purpose. However, the latter process occurred at the expense of considerable damage to the cellulose structure. The whiskers obtained by acid hydrolysis resulted in nanostructures with lower diameter and length, and high crystallinity. Increasing hydrolysis reaction time led to narrower and shorter whiskers, but increased the crystallinity index. The present work contributes to the different widespread methods used for the production of micro/nanofibres for different applications. (C) 2012 Elsevier Ltd. All rights reserved.

Processing-structure-property relationships in solid-state shear pulverization: Parametric study of specific energy

Solid-state shear pulverization (SSSP) is a unique processing technique for mechanochemical modification of polymers, compatibilization of polymer blends, and exfoliation and dispersion of fillers in polymer nanocomposites. A systematic parametric study of the SSSP technique is conducted to elucidate the detailed mechanism of the process and establish the basis for a range of current and future operation scenarios. Using neat, single component polypropylene (PP) as the model material, we varied machine type, screw design, and feed rate to achieve a range of shear and compression applied to the material, which can be quantified through specific energy input (Ep). As a universal processing variable, Ep reflects the level of chain scission occurring in the material, which correlates well to the extent of the physical property changes of the processed PP. Additionally, we compared the operating cost estimates of SSSP and conventional twin screw extrusion to determine the practical viability of SSSP.

Processing-Structure-Property Relationships in Solid-State Shear Pulverization: Parametric Study of specific energy

Solid-state shear pulverization (SSSP) is a unique processing technique for mechanochemical modification of polymers, compatibilization of polymer blends, and exfoliation and dispersion of fillers in polymer nanocomposites. A systematic parametric study of the SSSP technique is conducted to elucidate the detailed mechanism of the process and establish the basis for a range of current and future operation scenarios. Using neat, single component polypropylene (PP) as the model material, we varied machine type, screw design, and feed rate to achieve a range of shear and compression applied to the material, which can be quantified through specific energy input (Ep). As a universal processing variable, Ep reflects the level of chain scission occurring in the material, which correlates well to the extent of the physical property changes of the processed PP. Additionally, we compared the operating cost estimates of SSSP and conventional twin screw extrusion to determine the practical viability of SSSP.

Preparation and characterization of polyester resin-layered silicate containing reactive groups

Polymer nanocomposites, specifically nanoclay-reinforced polymers, have attracted great interest as matrix materials for high temperature composite applications. Nanocomposites require relatively low dispersant loads to achieve significant property enhancements. These enhancements are mainly a consequence of the interfacial effects that result from dispersing the silicate nanolayers in the polymer matrix and the high in-plane strength, stiffness and aspect ratio of the lamellar nanoparticles. The montmorillonite (MMT) clay, modified with organic onium ions with long alkyl chains as Cloisites, has been widely used to obtain nanocomposites. The presence of reactive groups in organic onium ions can form chemical bonds with the polymer matrix which favours a very high exfoliation degree of the clay platelets in the nanocomposite (1,2)