Solid-state modification of isotactic polypropylene (iPP) via grafting of styrene. II. Morphology and melt processing

Grafting of vinyl monomers onto isotactic polypropylene (iPP) in the solid state represents a convenient route to chemically modify iPP and, consequently, its properties. Solid-state modification can be carried out on iPP powder directly from the polymerization reactor. The modified powder is then processed in the melt, usually with the addition of fillers and/or additives, to obtain the final product. In this work we have studied the effect of melt processing on the morphology of solid-state polymerized PP/polystyrene (PS) blends, i.e., of a iPP powder previously modified in the solid-state with styrene (St) and optionally in the presence of divinylbenzene (DVB). A series of samples containing different amounts of PS and displaying different grafting efficiencies were investigated before and after processing in the melt. Transmission electron microscopy, scanning electron microscopy, and solid-state NMR were used to investigate the morphology on different length scales. It was shown that PS coalescence during processing can be hindered, thereby stabilizing the initially polymerized iPP/PS blends morphology. Indeed, reducing the PS amount in the blend or increasing the grafting efficiency resulted in less coalescence of the PS domains. Crosslinking of the PS phase during the solid-state polymerization resulted also in a very fine but heterogeneous morphology. (c) 2005 Wiley Periodicals, Inc

Influence of the polymer degradation on enhanced oil recovery processes

Polymer flooding is one of the most common and technically developed chemical Enhanced Oil Recovery (EOR) processes. Its main function is to increase the carrying phase's (i.e., water or brine) viscosity in order to mobilize the remaining trapped oil. Many numerical simulators have been developed during the last 30 years considering the influence of the polymer molecules on the viscosity as well as on other physical parameters (e.g., diffusion, adsorption). Nevertheless, there are certain phenomena which were not previously considered, for instance, the interfacial effects of hydrophobically modified polymers. Furthermore, the degradation of the polymer molecules in a harsh environment such as the one found in porous media is well known. This causes a deterioration on the viscosifying properties, diminishing the efficiency of the method. It is important also to consider the effect of the polymer viscoelasticity on the microscopic sweeping efficiency, lowering the residual oil saturation, which has not been properly addressed. A new compositional 2D numerical simulator is presented for polymer flooding in a two-phase, three-component configuration, considering all these physical effects present in porous media and using a fully second-order accurate scheme coupled with total variation diminishing (TVD) functions. Results demonstrated that degradation cannot be considered negligible in any polymer EOR process, since it affected the viscoelastic and viscosifying properties, decreasing the sweeping efficiency at both micro- and macroscopic scales. This simulator will allow setting the desired designing properties for future polymers in relationship with the characteristics of the oil field to be exploited

Influence of the polymer properties and numerical schemes on tertiary oil recovery processes

Chemical Enhanced Oil Recovery (EOR) processes comprise a number of flooding techniques aimed at increasing the operational life of mature oilfields. Among these, polymer flooding is one of the most developed; its functionality is to increment the aqueous viscosity, avoiding the formation of viscous fingering. Reservoir simulators consider this influence as well as other physical properties (e.g., adsorption, permeability reduction). However, the polymer degradation is usually not considered even though it plays a critical role in the viscosity. In this paper this mechanism is analyzed and coupled with the previously mentioned physical phenomena in order to present a complete study of their influence in the EOR process. Moreover, since a fully second-order accuracy scheme is used along with a Total Variation Diminishing (TVD) flux-limiting function, the influence of the latter on the recovery factor is also discussed. Results showed that the negative effect of the polymer adsorption was the most relevant physical phenomenon in terms of the oil recovery. Furthermore, the analysis of the discretization of the differential equations showed that traditional, linear first-order schemes created numerical diffusion affecting negatively the macroscopic sweeping efficiency, which disappeared when TVD techniques were used. Reservoir simulators allow determining the desired designing properties for future polymers in relationship with the characteristics of the oilfield to be exploited

Branched polymers and nanoparticles flooding as separate processes for enhanced oil recovery

Since it was first theorized more than half-century ago, nanotechnology has proven to be the perfect boost for existing technologies and the oil industry has made use of this avant-garde discipline to upsurge the productivity of mature oilfields. With respect to polymer flooding, recent research has stressed the importance of the (macro) molecules' architecture on the physical properties. This paper presents the numerical simulation of these two agents in standard, not combined, oil recovery processes. The polymer solution viscosity is calculated considering the polymer's architecture, its degradation and the salinity. The nanoparticles affect the carrier-phase viscosity and the rock formation wettability, which modifies the oil mobility. Results evidenced the improved capabilities of branched (i.e. star/comb) polymers with respect to traditional linear ones. The modified architecture improves not only the rheological but also the viscoelastic properties, which ultimately increases the microscopic sweeping efficiency. Nanoparticles increase slightly the carrier phase viscosity, but their main recovery mechanism is their adsorption onto the rock and subsequent wettability modification, reducing the residual oil saturation. Furthermore, it is also important to properly characterize both the particles' average size and also their aggregation rate, since these affect the recovery efficiency. Simulations show the importance of a good characterization of oil recovery agents and their effect on the phases' physical properties as well as the potential of nanoparticles to act as a boost of traditional enhanced recovery processes

Chemical enhanced oil recovery and the role of chemical product design

The current and prospective worldwide energy demands have led either to start exploiting the more difficult and costly unconventional oil reserves, or to maximize the exploitation of conventional oil sources. This triggered the development of enhanced oil recovery processes in order to improve the efficiency and lifetime of mature oilfields. Chemical Enhanced Oil Recovery is one of the most interesting group of methods nowadays. The use of chemical products such as polymers, surfactants, alkalis and polymeric surfactants has been continuously increasing during the last decades. However, these chemicals should be designed to withstand the harsh conditions present in the reservoir (e.g., dissolved salts, pH, temperature, presence of bacteria) and increase the efficiency of the process. One of the key factors in this development is the (macro)molecules’ architecture and its influence on the physical properties of the fluids being injected: from linear to branched polymers, from monomeric to gemini surfactants. Furthermore, the combination of these chemicals has showed a great potential due to the synergy between them, creating a new spectrum of techniques in chemical Enhanced Oil Recovery. This review presents the work done in this field with an analysis of the products and technologies employed, including their limitations and possible ways to improve their performance. All in all, the need of advanced products for oil recovery and new, or improved, energy sources has set off a new field of research wherein chemical product engineering plays a major role

Predictive validity of the HCR-20 for inpatient aggression:the effect of intellectual disability on accuracy

BackgroundPeople with intellectual disability (ID) account for a large proportion of aggressive incidents in secure and forensic psychiatric services. Although the Historical, Clinical, Risk Management 20 (HCR-20) has good predictive validity in inpatient settings, it does not perform equally in all groups and there is little evidence for its efficacy in those with ID.MethodA pseudo-prospective cohort study of the predictive efficacy of the HCR-20 for those with ID (n = 109) was conducted in a UK secure mental health setting using routinely collected risk data. Performance of the HCR-20 in the ID group was compared with a comparison group of adult inpatients without an ID (n = 504). Analysis controlled for potential covariates including security level, length of stay, gender and diagnosis.ResultsThe HCR-20 total score was a significant predictor of any aggression and of physical aggression for both groups, although the area under the curve values did not reach the threshold for a large effect size. The clinical subscale performed significantly better in those without an ID compared with those with. The ID group had a greater number of relevant historical and risk management items. The clinicians' summary judgment significantly predicted both types of aggressive outcomes in the ID group, but did not predict either in those without an ID.ConclusionsThis study demonstrates that, after controlling for a range of potential covariates, the HCR-20 is a significant predictor of inpatient aggression in people with an ID and performs as well as for a comparison group of mentally disordered individuals without ID. The potency of HCR-20 subscales and items varied between the ID and comparison groups suggesting important target areas for improved prediction and risk management interventions in those with ID

Design of a pH-responsive conductive nanocomposite based on MWCNTs stabilized in water by amphiphilic block copolymers

Homogeneouswater dispersions ofmulti-walled carbon nanotubes (MWCNTs)were prepared by ultrasonication in the presence of an amphiphilic polystyrene-block-poly(acrylic acid) (PS-b-PAA) copolymer. The ability of PS-b-PAA to disperse and stabilizeMWCTNs was investigated by UV-vis, SEM and zeta potential. The results show that the addition of a styrene block to PAA enhances the dispersion efficiency of the graphitic filler compared to pure PAA, possibly due to the nanotube affinity with the polystyrene moiety. Notably, the dispersions show an evident pH-responsive behavior, being MWCNTs reaggregation promoted in basic environment. It isworth noting that the responsive character is maintained in solid composites obtained by drop casting, thus indicating potential applications in sensing

Supercritical carbon dioxide as a green solvent for processing polymer melts:Processing aspects and applications

Supercritical carbon dioxide (CO(2)) is Well established for use as a processing solvent in polymer applications such as polymer modification, formation of polymer composites, polymer blending, microcellular foaming, particle production and polymerization. Its gas-like diffusivity and liquid-like density in the supercritical phase allow replacing conventional, often noxious, solvents with supercritical CO(2). Though only a few polymers are soluble in supercritical CO(2), it is quite soluble in many molten polymers. CO(2) dissolution in a polymer has been interpreted physically but FT-IR studies lead to an explanation in terms of weak interactions between basic and acidic sites. Various experimental methods and equations of state are available to measure or predict the solubility of CO(2). Dissolved CO(2) causes a considerable reduction in the viscosity of molten polymer, a very important property for the applications stated above. CO(2) mainly acts as a plasticizer or solvent when contacted with a polymer. Gas solubility and viscosity reduction can be predicted theoretically from pure-component properties. In this review, experimental and theoretical studies of solubility and viscosity of several polymer melts are discussed in detail. Detailed attention is also given to recently reported applications along with aspects related to polymer processing. (c) 2005 Elsevier Ltd. All rights reserved

Solid-State Modification of Polypropylene (PP):Grafting of Styrene on Atactic PP

Grafting of unsaturated vinyl monomers onto polypropylene (PP) is a convenient route to develop new polymeric materials with synergistic properties. Particular attention must be paid to the formation of graft copolymer relative to the formation of homopolymer, since the final properties are dependent both on the dispersion of the new polymer into the iPP matrix, which is controlled by the degree of grafting, as well as on the chemical nature of the in-situ formed polymer chains. In the present work the grafting reaction of styrene on atactic PP (aPP), considered as good model system for the more studied solid-state modification of isotactic PP (iPP), has been investigated in the presence of two different radical initiators in order to get a first insight into the grafting reactions onto PP. Several grafting reactions were carried out by changing the chemical compositions of the starting polymerization mixture, whose homogeneity was accurately investigated by Raman spectroscopy. Infrared-spectroscopy (FT-IR) was used for qualitative and quantitative characterization of the reaction product. A quantitative separation procedure, based on the concept of selective solvent extraction, has been established which enables the determination of the grafting efficiency (Φ) as well as the exact chemical composition of the final product. Finally, all products were characterized by means of Differential Scanning Calorimetry (DSC) in order to study their thermal behaviour