Promoting carbonization of polypropylene during combustion through synergistic catalysis of a trace of halogenated compounds and Ni2O3 for improving flame retardancy

The effect of combination between a trace of halogenated compounds (such as ferric chloride and ammonium bromide) and Ni2O3 particles on the carbonization of polypropylene (PP) was investigated during combustion. The results showed a synergistic catalysis of combined halogenated compounds with Ni2O3 in promoting the formation of the residual char during combustion. The investigation on the promotion mechanism showed that halide radical releasing from halogen-containing additives worked as a catalyst to accelerate dehydrogenation-aromatization of degradation products of PR which promote the degradation products to form the residual char catalyzed by nickel catalyst.

Combination of Carbon Nanotubes with Ni2O3 for Simultaneously Improving the Flame Retardancy and Mechanical Properties of Polyethylene

Effects of multiwalled carbon nanotubes (MWCNTs) and Ni2O3 on the flame retardancy of linear low density polyethylene (LLDPE) have been studied. A combination of MWCNTs and Ni2O3 showed a synergistic effect in improving the flame retardancy of LLDPE compared with LLDPE composites containing MWCNTs or Ni2O3 alone. As a result, the peak value of heat release rate measured by cone calorimeter was obviously decreased in the LLDPE/MWCNTs/Ni2O3 Composites. According to the results from rheological tests, carbonization experiments, and structural characterization of residual char, the improved flame retardancy was partially attributed to the formation of a networklike structure due to the good dispersion of MWCNTs in LLDPE matrix, and partially to the carbonization of degradation products of LLDPE catalyzed by Ni catalyst originated from Ni2O3, More importantly, both viscoelastic characteristics and catalytic carbonization behavior of LLDPE/MWCNTs/Ni2O3 composites acted in concert to result in a synergistic effect in improving the flame retardancy.

Biaxial deformation behavior and mechanical properties of a polypropylene/clay nanocomposite

Polymer nanocomposites offer the potential of enhanced properties such as increased modulus and barrier properties to the end user. Much work has been carried out on the effects of extrusion conditions on melt processed nanocomposites but very little research has been conducted on the use of polymer nanocomposites in semi-solid forming processes such as thermoforming and injection blow molding. These processes are used to make much of today’s packaging, and any improvements in performance such as possible lightweighting due to increased modulus would bring signi?cant bene?ts both economically and environmentally. The work described here looks at the biaxial deformation of polypropylene–clay nanocomposites under industrial forming conditions in order to determine if the presence of clay affects processability, structure and mechanical properties of the stretched material. Melt compounded polypropylene/clay composites in sheet form were biaxially stretched at a variety of processing conditions to examine the effect of high temperature, high strain and high strain rate processing on sheet structure
and properties.

A biaxial test rig was used to carry out the testing which imposed conditions on the sheet that are representative of those applied in injection blow molding and thermoforming. Results show that the presence of clay increases the yield stress relative to the un?lled material at typical processing temperatures and that the sensitivity of the yield stress to temperature is greater for the ?lled material. The stretching process is found to have a signi?cant effect on the delamination and alignment of clay particles (as observed by TEM) and on yield stress and elongation at break of the stretched sheet.

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.

Conductivity in amorphous polyether nanocomposite materials

Using a completely amorphous polyether we have investigated the effect of the inclusion of a nano-particulate filler on a polymer electrolyte. Nano-sized TiO₂ is shown not to significantly affect the conductivity of composite electrolytes containing 1.0 or 1.25 mol/kg LiClO₄ or 1.5 or 2.0 mol/kg LiTFSI. At 1.5 mol/kg LiClO₄ a significant increase in conductivity is observed. Raman spectroscopy experiments have been used to investigate the effect of filler on ion-aggregation. Only one new vibrational mode can be assigned to the composite which is not due to the polymer electrolyte or the filler. From this work, we believe the increased conductivity observed by previous researchers as a result of filler addition may be largely attributed to the effect on the degree of crystallinity along with some disruption of ion-aggregation by the fillers in PEO based electrolytes.

Bioinspired strategy to reinforce PVA with improved toughness and thermal properties via hydrogen-bond self-assembly

Despite the high strength and stiffness of polymer nanocomposites, they usually display lower deformability and toughness relative to their matrices. Spider silk features exceptionally high stiffness and toughness via the hierarchical architecture based on hydrogen-bond (H-bond) assembly. Inspired by this intriguing phenomenon, we here exploit melamine (MA) to reinforce poly(vinyl alcohol) (PVA) via H-bond self-assembly at a molecular level. Our results have shown that due to the formation of physical cross-link network based on H-bond assembly between MA and PVA, yield strength, Young’s modulus, extensibility, and toughness of PVA are improved by 22, 25, 144, and 200% with 1.0 wt % MA, respectively. Moreover, presence of MA can enhance the thermal stability of PVA to a great extent, even exceeding some nanofillers (e.g., graphene). This work provides a facile method to improve the mechanical properties of polymers via H-bond self-assembly.

Carbon nanotube based elastomer composites-an approach towards multifunctional materials

The current study focuses on giving a basic understanding of tubular graphene sheets or carbon nanotubes (CNTs) and points towards their role in fabricating elastomer composites. Since the properties and the performance of CNT reinforced elastomer composites predominantly depend on the rate of dispersion of fillers in the matrix, the physical and chemical interaction of polymer chains with the nanotubes, crosslinking chemistry of rubbers and the orientation of the tubes within the matrix, here, a thorough study of these topics is carried out. For this, various techniques of composite manufacturing such as pulverization, heterocoagulation, freeze drying, etc. are discussed by emphasizing the dispersion and alignment of CNTs in elastomers. The importance of the functionalization technique as well as the confinement effect of nanotubes in elastomer media is derived. In a word, this article is aimed exclusively at addressing the prevailing problems related to the CNT dispersion in various rubber matrices, the solutions to produce advanced high-performance elastomeric composites and various fields of applications of such composites, especially electronics. Special attention has also been given to the non-linear viscoelasticity effects of elastomers such as the Payne effect, Mullin's effect and hysteresis in regulating the composite properties. Moreover, the current challenges and opportunities for efficiently translating the extraordinary electrical properties of CNTs to rubbery matrices are also dealt with.

Synergistic effect of multi walled carbon nanotubes and reduced graphene oxides in natural rubber for sensing application

Utilizing the electrical properties of polymer nanocomposites is an important strategy to develop high performance solvent sensors. Here we report the synergistic effect of multi walled carbon nanotubes (MWCNTs) and reduced graphene oxide (RGO) in regulating the sensitivity of the naturally occurring elastomer, natural rubber (NR). Composites were fabricated by dispersing CNTs alone and together with exfoliated RGO sheets (thermally reduced at temperatures of 200 and 600 °C) in NR by a solution blending method. RGO exfoliation and the uniform distribution of fillers in the composites were studied by atomic force microscopy, Fourier transformation infrared spectroscopy, X-ray diffraction, transmission electron microscopy and Raman spectroscopy. The solvent sensitivity of the composite samples was noted from the sudden variation in electrical conductivity which was due to the breakdown of the filler networks during swelling in different solvents. It was found that the synergy between CNTs and RGO exfoliated at 200 °C imparts maximum sensitivity to NR in recognizing the usually used aromatic laboratory solvents. Mechanical and dynamic mechanical studies reveal efficient filler reinforcement, depending strongly on the nature of filler-elastomer interactions and supports the sensing mechanism. Such interactions were quantitatively determined using the Maier and Göritz model from Payne effect experiments. It is concluded that the polarity induced by RGO addition reduces the interactions between CNTs and ultimately results in the solvent sensitivity. © 2013 The Royal Society of Chemistry.

Bio-inspired hydrogen-bond cross-link strategy toward strong and tough polymeric materials

It remains a huge challenge to create advanced polymeric materials combining high strength, great toughness, and biodegradability so far. Despite enhanced strength and stiffness, biomimetic materials and polymer nanocomposites suffer notably reduced extensibility and toughness when compared to polymer bulk. Silk displays superior strength and toughness via hydrogen bonds (H-bonds) assembly, while cuticles of mussels gain high hardness and toughness via metal complexation cross-linking. Here, we propose a H-bonds cross-linking strategy that can simultaneously strikingly enhance strength, modulus, toughness, and hardness relative to polymer bulk. The H-bond cross-linked poly(vinyl alcohol) exhibits high yield strength (140 MPa), reduced modulus (22.5 GPa) in nanoindention tests, hardness (0.5 GPa), and great extensibility (40%). More importantly, there exist semiquantitive linear relationships between the number of effective H-bond and macroscale properties. This work suggests a promising methodology of designing advanced materials with exceptional mechanical by adding low amounts (1.0 wt %) of small molecules multiamines serving as H-bond cross-linkers.

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.