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  • 1.
    Akhlaghi, Shahin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Amir Masoud, Pourrahimi
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Christian, Sjöstedt
    Martin, Bellander
    Mikael S., Hedenqvist
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Ulf W., Gedde
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Degradation of fluoroelastomers in rapeseed biodiesel at different oxygen concentrations2017In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 136, p. 10-19Article in journal (Refereed)
    Abstract [en]

    The degradation of fluoroelastomers (FKM) based on different monomers, additives and curing systems was studied after exposure to rapeseed biodiesel at 100 °C and different oxygen partial pressures. The sorption of fuel in the carbon black-filled FKM terpolymer was promoted by the fuel-driven cavitation in the rubber. The bisphenol-cured rubbers swelled more in biodiesel than the peroxide-cured FKM, presumably due to the chain cleavage caused by the attack of biodiesel on the double bonds formed during the bisphenol curing. With any of the selected types of monomer, the FKM rubbers absorbed biodiesel faster and to a greater extent with increasing oxygen partial pressure due to the increase in concentration of the oxidation products of biodiesel. Water-assisted complexation of biodiesel on magnesium oxide and calcium hydroxide particles led to dehydrofluorination of FKM, resulting in an extensive fuel uptake and a decrease in the strain-at-break and the Young's modulus of the rubbers. An increase in the CH2-concentration determined by infrared spectroscopy, and the appearance of biodiesel flakes in scanning electron micrographs of the extracted rubbers, were explained as being due to the presence of insoluble biodiesel grafted onto FKM on the unsaturated sites resulting from dehydrofluorination. The extensibility of the GFLT-type FKM was the least affected on exposure to biodiesel because this rubber contained less unsaturation and metal oxide/hydroxide particles.

  • 2.
    Akhlaghi, Shahin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials. Scania CV AB, Sweden.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Brana, Maria T. Conde
    Bellander, Martin
    Deterioration of automotive rubbers in liquid biofuels: A review2015In: Renewable & sustainable energy reviews, ISSN 1364-0321, E-ISSN 1879-0690, Vol. 43, p. 1238-1248Article, review/survey (Refereed)
    Abstract [en]

    Concerns over the fast depletion of fossil fuels, environmental issues and stringent legislation associated with petroleum-based fuels have triggered a shift to bio-based fuels, as an alternative to meet the growing energy demand in the transportation sector. However, since conventional automobile fuel systems are adapted to petroleum-based fuels, switching to biofuels causes a severe deterioration in the performance of currently used rubber components. The degradation of the rubber materials in biofuels is complicated by the presence of different additives in biofuels and rubber compounds, by oxidation of biofuels and by the effects of thermomechanical loadings in the engine. This paper presents a comprehensive review of the effects of different types of biofuels, particularly biodiesel and bioethanol, on the physical, mechanical, morphological and thermal properties of elastomers under different exposure conditions. In addition, the literature data available on the variation of rubbers' resistance to biofuels with the changes in their monomer type and composition, cure system and additives content was also studied. The review essentially focuses on the compatibility of biofuels with acrylonitrile butadiene rubber, fluoroelastomers, polychloroprene rubber and silicon rubber, as the most commonly used automotive rubbers coming into contact with fuels during their service. The knowledge summarized in this study can help to develop a guideline on the selection of rubber for automotive parts designed to withstand biofuels.

  • 3.
    Akhlaghi, Shahin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Brana, M. T. Conde
    Bellander, M.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Deterioration of acrylonitrile butadiene rubber in rapeseed biodiesel2015In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 111, p. 211-222Article in journal (Refereed)
    Abstract [en]

    The deterioration of acrylonitrile butadiene rubber (NBR) exposed to rapeseed biodiesel at 90 degrees C was studied. The oxidation of biodiesel and NBR during ageing was monitored by H-1 NMR and infrared spectroscopy, HPLC and titration methods. The oxidation of biodiesel was impeded in the presence of NBR, but promoted in biodiesel-exposed rubber. This was explained as being due to the migration of stabilizer from the rubber to biodiesel, the diffusion of dissolved oxygen from biodiesel into NBR and the absorption of oxidation precursors of biodiesel by the rubber. The resemblance between the anomalous sorption kinetics of biodiesel in NBR and the equilibrium benzene uptake by the aged rubbers revealed that biodiesel caused a network defect in NBR, resulting in a gradual increase in the equilibrium swelling. The cleavage of crosslinks was implausible since the Young's modulus of the rubber at low strains, disregarding an initial decrease, increased with increasing exposure time. The appearance of 'naked' carbon black particles in the scanning electron micrographs of the aged rubbers and a drastic decrease in the strain-at-break of NBR after exposure to biodiesel suggests that internal cavitation was caused by the attack of biodiesel on the acrylonitrile units of NBR.

  • 4.
    Akhlaghi, Shahin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Pourrahimi, A. M.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Christian, Sjöstedt
    Martin, Bellander
    Mikael S., Hedenqvist
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Ulf W., Gedde
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Effects of ageing conditions on degradation of acrylonitrile butadiene rubber filled with heat-treated ZnO star-shaped particles in rapeseed biodiesel2017In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321Article in journal (Refereed)
    Abstract [en]

    The degradation of acrylonitrile butadiene rubber (NBR) after exposure to biodiesel at different oxygen partial pressures in an automated ageing equipment at 80 °C, and in a high-pressure autoclave at 150 °C was studied. The oxidation of biodiesel was promoted by an increase in oxygen concentration, resulting in a larger uptake of fuel in the rubber due to internal cavitation, a greater decrease in the strain-at-break of NBR due to the coalescence of cavity, and a faster increase in the crosslinking density and carbonyl index due to the promotion of the oxidation of NBR. During the high-temperature autoclave ageing, less fuel was absorbed in the rubber, because the formation of hydroperoxides and acids was impeded. The extensibility of NBR aged in the autoclave decreased only slightly due to the cleavage of rubber chains by the biodiesel attack. The degradation of NBR in the absence of carbon black was explained as being due to oxidative crosslinking. The dissolution of ZnO crystals in the acidic components of biodiesel was retarded by removing the inter-particle porosity and surface defects through heat treating star-shaped ZnO particles. The rubber containing heat-treated ZnO particles swelled less in biodiesel than a NBR filled with commercial ZnO nanoparticles, and showed a smaller decrease in the strain-at-break and less oxidative crosslinking.

  • 5.
    Akhlaghi, Shahin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Pourrahimi, Amir Masoud
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Sjöstedt, C.
    Bellander, M.
    Gedde, Ulf
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Degradation of carbon-black-filled acrylonitrile butadiene rubber in alternative fuels: Transesterified and hydrotreated vegetable oils2016In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 123, p. 69-79Article in journal (Refereed)
    Abstract [en]

    The deterioration of acrylonitrile butadiene rubber (NBR), a common sealing material in automobile fuel systems, when exposed to rapeseed biodiesel and hydrotreated vegetable oil (HVO) was studied. The fuel sorption was hindered in HVO-exposed rubber by the steric constraints of bulky HVO molecules, but it was promoted in biodiesel-exposed rubber by fuel-driven cavitation in the NBR and by the increase in diffusivity of biodiesel after oxidation. The absence of a tan δ peak of the bound rubber and the appearance of carbon black particles devoid of rubber suggested that the cavitation was made possible in biodiesel-aged rubber by the detachment of bound rubber from particle surfaces. The HVO-exposed NBR showed a small decrease in strain-at-break due to the migration of plasticizer from the rubber, and a small increase in the Young’s modulus due to oxidative crosslinking. A drastic decrease in extensibility and Payne-effect amplitude of NBR on exposure to biodiesel was explained as being due to the damage caused by biodiesel to the continuous network of bound rubber-carbon black. A decrease in the ZnO crystal size with increasing exposure time suggested that the particles are gradually dissolved in the acidic components of oxidized biodiesel. The Zn2+ cations released from the dissolution of ZnO particles in biodiesel promoted the hydrolysis of the nitrile groups of NBR.

  • 6.
    Alipour, Nazanin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Andersson, Richard L.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Olsson, Richard T.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    VOC-Induced Flexing of Single and Multilayer Polyethylene Films As Gas Sensors2016In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 8, no 15, p. 9946-9953Article in journal (Refereed)
    Abstract [en]

    The differential swelling and bending of multilayer polymeric films due to the dissimilar uptake of volatile organic compounds (VOCs; n-hexane, limonene) in the different layers was studied. Motions of thin polyethylene films triggered by the penetrant were investigated to learn more about how their deformation is related to VOC absorption. Single layers of metallocene or low-density polyethylene, and multilayers (2-288-layers) of these in alternating positions were considered. Single-, 24-, and 288 layer films displayed no motion when uniformly subjected to VOCs, but they could display simple curving modes when only one side of the film was wetted with a liquid VOC. Two-layer films displayed simple bending when uniformly subjected to VOCs due to the different swelling in the two layers, but when the VOC was applied to only one side of the film, more complex modes of motion as well as dynamic oscillations were observed (e.g., constant amplitude wagging at 2 Hz for ca. 50 s until all the VOC had evaporated). Diffusion modeling was used to study the transport behavior of VOCs inside the films and the different bending modes. Finally a prototype VOC sensor was developed, where the reproducible curving of the two-layer film was calibrated with n-hexane. The sensor is simple, cost-efficient, and nondestructive and requires no electricity.

  • 7.
    Alipour, Nazanin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Yu, Shun
    Roth, Stephan
    Brüning, Karsten
    Vieyres, Arnaud
    Schneider, Konrad
    Structure and properties of polyethylene-based and EVOH-based multilayered films with layer thicknesses of 150 nm and greater2015In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 64, p. 36-51Article in journal (Refereed)
    Abstract [en]

    This paper presents the structure and properties of two multilayered systems where polymers in adjacent layers were either miscible or immiscible. The miscible system consisted of 2, 17, 18, 24 and nominally 288 layers of alternating low-density (LDPE) and low-density/linear-low density (mPE) polyethylene layers with observed thicknesses ranging from 150 nm to 20 urn. The immiscible system consisted of 5 and 19 layer films with a combination of poly(ethylene-co-vinyl alcohol) (EVOH) (thickness: 9 and 1 gm, respectively), LDPE (17 and 7 gm) and a polyethylene adhesive (3 and 1 gm). The purpose of the multi-layering was to increase the crack growth resistance and, in the EVOH-based system, to decrease the oxygen transmission rate. Indeed, the crack growth resistance, as measured on tensile-tested notched films, increased with increasing number of layers. The thinnest polyethylene and polyethylene adhesive layers showed a clear ductile failure when fractured even in liquid nitrogen. Simultaneous synchrotron wide-angle/small-angle X-ray scattering and tensile testing indicated no new deformation features with changes in the layer thickness. The oxygen permeability was the same in the 5- and 19-layer EVOH-based films, but the uptake of n-hexane was strongly reduced in the 19-layer films, demonstrating the effective protective role of the EVOH layers. The n-hexane desorption data of the 2-layer LDPE/mPE film was successfully modeled using the diffusivities and solubilities of the single layers. Crystallization was slower and more confined in the films with thinner layers. The interlayer mixing in the melt (measured by isothermal crystallization from melts of initially layered polyethylene-based systems) was, as expected, significantly faster in the 24- and 288-multilayer films than in the 2-layer film.

  • 8. Amanizadeh, Farhad
    et al.
    Akhlaghi, Shahin
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Mobarakeh, Hamid Salehi
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Starve fed emulsion copolymerization of vinyl acetate and 1-hexene at ambient pressure2014In: Polymer international, ISSN 0959-8103, E-ISSN 1097-0126, Vol. 63, no 10, p. 1850-1855Article in journal (Refereed)
    Abstract [en]

    A novel emulsion copolymer of vinyl acetate (VAc) and 1-hexene was synthesized at ambient pressure. The feeding technique, initiation system and reaction time of the copolymerization were optimized based on molecular characteristics such as the weight contribution of 1-hexene in the copolymer chains and glass transition temperature (T-g) as well as on bulk properties like minimum film-formation temperature (MFFT) and solid content. According to nuclear magnetic resonance spectroscopy and differential scanning calorimetry results, the combination of starve feeding and redox initiation, within a reaction time of 4h, effectively led to the copolymerization at ambient pressure between highly reactive polar VAc monomers and non-polar 1-hexene monomers of low reactivity. The copolymer showed a lower T-g and MFFT, and a reasonable solid content compared to the poly(vinyl acetate) (PVAc) homopolymer. The consumption rate, hydrolysis of acetate groups and chain transfer reactions during the polymerization were followed using infrared spectroscopy. Based on the results, the undesirable reactions between the VAc blocks were hindered by the neighbouring 1-hexene molecules. Tensile testing revealed an improvement in the toughness and elongation at break of VAc-1-hexene films compared to PVAc films.

  • 9.
    Andersson, Richard L.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Martinez-Abad, Antonio
    Lagaron, Jose M.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Mallon, Peter E.
    Olsson, Richard T.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Antibacterial Properties of Tough and Strong Electrospun PMMA/PEO Fiber Mats Filled with Lanasol-A Naturally Occurring Brominated Substance2014In: International Journal of Molecular Sciences, ISSN 1422-0067, E-ISSN 1422-0067, Vol. 15, no 9, p. 15912-15923Article in journal (Refereed)
    Abstract [en]

    A new type of antimicrobial, biocompatible and toughness enhanced ultra-thin fiber mats for biomedical applications is presented. The tough and porous fiber mats were obtained by electrospinning solution-blended poly (methyl methacrylate) (PMMA) and polyethylene oxide (PEO), filled with up to 25 wt % of Lanasol-a naturally occurring brominated cyclic compound that can be extracted from red sea algae. Antibacterial effectiveness was tested following the industrial Standard JIS L 1902 and under agitated medium (ASTM E2149). Even at the lowest concentrations of Lanasol, 4 wt %, a significant bactericidal effect was seen with a 4-log (99.99%) reduction in bacterial viability against S. aureus, which is one of the leading causes of hospital-acquired (nosocomial) infections in the world. The mechanical fiber toughness was insignificantly altered up to the maximum Lanasol concentration tested, and was for all fiber mats orders of magnitudes higher than electrospun fibers based on solely PMMA. This antimicrobial fiber system, relying on a dissolved antimicrobial agent (demonstrated by X-ray diffraction and Infrared (IR)-spectroscopy) rather than a dispersed and "mixed-in" solid antibacterial particle phase, presents a new concept which opens the door to tougher, stronger and more ductile antimicrobial fibers.

  • 10.
    Andersson, Richard L.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Ström, Valter
    KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Engineering Material Physics.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Mallon, Peter E.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Olsson, Richard T.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Micromechanics of ultra-toughened electrospun PMMA/PEO fibres as revealed by in-situ tensile testing in an electron microscope2014In: Scientific Reports, ISSN 2045-2322, E-ISSN 2045-2322, Vol. 4, p. 6335-Article in journal (Refereed)
    Abstract [en]

    A missing cornerstone in the development of tough micro/nano fibre systems is an understanding of the fibre failure mechanisms, which stems from the limitation in observing the fracture of objects with dimensions one hundredth of the width of a hair strand. Tensile testing in the electron microscope is herein adopted to reveal the fracture behaviour of a novel type of toughened electrospun poly(methyl methacrylate)/poly(ethylene oxide) fibre mats for biomedical applications. These fibres showed a toughness more than two orders of magnitude greater than that of pristine PMMA fibres. The in-situ microscopy revealed that the toughness were not only dependent on the initial molecular alignment after spinning, but also on the polymer formulation that could promote further molecular orientation during the formation of micro/nano-necking. The true fibre strength was greater than 150 MPa, which was considerably higher than that of the unmodified PMMA (17 MPa). This necking phenomenon was prohibited by high aspect ratio cellulose nanocrystal fillers in the ultra-tough fibres, leading to a decrease in toughness by more than one order of magnitude. The reported necking mechanism may have broad implications also within more traditional melt-spinning research.

  • 11. Arabasadi, Z.
    et al.
    Khorasani, M.
    Akhlaghi, Shahin
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Fazilat, H.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Shiri, M. E.
    Prediction and optimization of fireproofing properties of intumescent flame retardant coatings using artificial intelligence techniques2013In: Fire safety journal, ISSN 0379-7112, E-ISSN 1873-7226, Vol. 61, p. 193-199Article in journal (Refereed)
    Abstract [en]

    A multi-structured architecture of artificial intelligence techniques including artificial neural network (ANN), adaptive neuro-fuzzy-inference-system (ANFIS) and genetic algorithm (GA) were developed to predict and optimize the fireproofing properties of a model intumescent flame retardant coating including ammonium polyphosphate, pentaerythritol, melamine, thermoplastic acrylic resin and liquid hydrocarbon resin. By implementing ANN on heat insulation results of coating samples, prepared based on a L16 orthogonal array, mean fireproofing time (MFPT) values were properly predicted. The predicted data were then proved to be valid through performing closeness examinations on fuzzy inference systems results regarding their experimental counterparts. However, the possible deviations tapped into phenomena like foam detachment and char cracking were alleviated by ANFIS modeling embedded with pertinent fuzzy rules based on the sole and associative practical role of used additives. The contribution of each intumescent coating component on the formulation with optimized fireproofing behavior was then explored using GA modeling. A similar optimization procedure was also conducted using conventional Taguchi experimental design but the GA based optimized intumescent coating was found to exhibit higher MFPT value than that suggested by the Taguchi method.

  • 12.
    Azhdar, Bruska
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Yu, Wenbin
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Reitberger, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Gedde, Ulf
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    A new method for assessing the efficiency of stabilizers in polyolefins exposed to chlorinated water media2009In: Polymer testing, ISSN 0142-9418, E-ISSN 1873-2348, Vol. 28, no 6, p. 661-667Article in journal (Refereed)
    Abstract [en]

    The chlorine used as disinfectant in tap water degrades most materials, including polyethylene. The most adequate (functional) test method, the pressure test, is complicated and expensive because the chlorinated aqueous media (Cl-2 or ClO2 in water) are unstable and they undergo reactions that are dependent on the pH. A new method which assesses the protection efficiency of phenolic antioxidants in polyolefins was developed. The method uses a liquid hydrocarbon analogue, squalane, in which antioxidants are dissolved. The organic phase was dispersed in the aqueous chlorinated phase (containing 10 ppm of either Cl-2 or ClO2; pH=6.8) at 70 degrees C by intense stirring. The depletion of antioxidant (Irganox 1010) was monitored by standard DSC determination of the oxidation induction time. It was shown that 300 min of exposure was sufficient to obtain useful data.

  • 13.
    Borgani, Riccardo
    et al.
    KTH, School of Engineering Sciences (SCI), Applied Physics, Nanostructure Physics.
    Pallon, Love
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Haviland, David
    KTH, School of Engineering Sciences (SCI), Applied Physics, Nanostructure Physics.
    Local Charge Injection and Extraction on Surface-Modified Al2O3Nanoparticles in LDPE2016In: Nano letters (Print), ISSN 1530-6984, E-ISSN 1530-6992, Vol. 16, no 9, p. 5934-5937, article id 10.1021/acs.nanolett.6b02920Article in journal (Refereed)
    Abstract [en]

    We use a recently developed scanning probe technique to image with high spatial resolution the injection and extraction of charge around individual surface-modified aluminum oxide nanoparticles embedded in a low-density polyethylene (LDPE) matrix. We find that the experimental results are consistent with a simple band structure model where localized electronic states are available in the band gap (trap states) in the vicinity of the nanoparticles. This work offers experimental support to a previously proposed mechanism for enhanced insulating properties of nanocomposite LDPE and provides a powerful experimental tool to further investigate such properties.

  • 14. Busson, P.
    et al.
    Ortegren, J.
    Ihre, H.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Hult, Anders
    KTH, Superseded Departments, Polymer Technology.
    Andersson, G.
    Ferroelectric liquid crystalline dendrimers: Synthesis, thermal behavior, and electrooptical characterization2001In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 34, no 5, p. 1221-1229Article in journal (Refereed)
    Abstract [en]

    The preparation and characterization of a series of novel ferroelectric liquid crystalline dendrimers are presented. End-capping of 1-, 2-, and 3-generation dendrimers based on 2,2-bis(hydroxymethyl)propionic acid with mesogens gave surface-functionalized liquid crystalline compounds with 6, 12, and 24 mesogen-containing units, respectively. 4 -((R)-1-Methylheptyloxy)phenyl 4-(4 '-[10(hydroxycarbonyl)decyloxyl phenyl)benzoate was synthesized and used as a mesogen-containing unit. The purity and structure of each compound were determined by H-1 NMR spectroscopy, size exclusion chromatography, and elemental analysis. Differential scanning calorimetry and optical microscopy were used to investigate the mesomorphic properties of the mesogen-functionalized dendrimers. The materials displayed a variety of mesophases, including the smectic C* phase. All the liquid crystalline dendrimers showed ferroelectricity, and tilt angle and spontaneous polarization measurements were performed. The obtained results show that the ferroelectric properties of the materials are independent of the generation number of the dendritic scaffold.

  • 15. Busson, P.
    et al.
    Ortegren, J.
    Ihre, H.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Hult, Anders
    KTH, Superseded Departments, Polymer Technology.
    Andersson, G.
    Eriksson, A.
    Lindgren, M.
    Preparation of mesogen-functionalized dendrimers for second-order nonlinear optics2002In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 35, no 5, p. 1663-1671Article in journal (Refereed)
    Abstract [en]

    Liquid crystalline dendrimers with peripheral mesogen-containing units have been prepared. Multistep synthesis with several selective reactions was used in the preparation of the mesogen-containing molecules, 4-[10-(hydroxycarbonyl)decyloxy]phenyl 4-[4'-(2-(R)-octyloxy)-3'-nitrophenyl]benzo ate and 4-[10-(hydroxycarbonyl)decyloxy]biphenyl 4-[4'-(2-(R)-octyloxy)-3'-nitrophenyl]benzoate. Both molecules possessed an electron-accepting nitro group placed perpendicular to the long axis of the molecules in order to enhance the nonlinear optical activity. A second generation hydroxyl functional aliphatic dendrimer based on the dihydroxy acid, 2,2-bis(hydroxymethyl)propionic acid, was used as dendritic scaffold and was subsequently functionalized with the aforementioned groups. The purity and structure of the two liquid crystalline dendrimers were determined by H-1 NMR spectroscopy, size exclusion chromatography, and elemental analysis. The synthesis of both the mesogen-containing units and the liquid crystalline dendrimers is described in detail. Investigation of the liquid crystalline properties of the materials by differential scanning calorimetry and optical microscopy showed that they exhibited different mesophases, including the chiral smectic C phase. Ferroelectric switching was observed in this tilted phase, and electrooptical properties, including tilt angle and spontaneous polarization measurements, were investigated. Finally, the nonlinear optical properties of one of the materials were preliminary characterized.

  • 16.
    Chen, Fei
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Gällstedt, M.
    Olsson, Rickard
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Gedde, Ulf
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    A novel chitosan/wheat gluten biofoam fabricated by spontaneous mixing and vacuum-drying2015In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 5, no 114, p. 94191-94200Article in journal (Refereed)
    Abstract [en]

    A new type of chitosan and wheat gluten biofoam is presented. The pore structure achieved relied solely on the specific mixing and phase distribution when a film was cast from an aqueous mixture of chitosan/wheat gluten solution, in the absence of any chemical blowing agent, porogen or expanding gas. The foam was obtained when the liquid phase was removed by vacuum drying, without the need for the traditional freeze-drying that is frequently used for pore formation. Soft foam samples could be prepared with stiffnesses from 0.3 to 1.2 MPa and a high rebound resilience (64 and 94% at compressive strains of 80 and 20%, respectively). The foams were relatively ductile and did not require any plasticiser to allow for in-plane deformation (20% compression) and smaller bending. Only open pores with sizes of the order of 70-80 μm were observed by microscopy. The density of all the foams was ∼50 kg m-3, due to the high porosity (96% air). The foams showed a rapid and large uptake of both non-polar (limonene) and polar (water) liquids. When immersed in these liquids for 1 second, the maximum uptake recorded was 40 times the initial mass of the foam for limonene and 8 times for water.

  • 17.
    Chen, Fei
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Gällstedt, Mikael
    Olsson, Richard
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Gedde, Ulf
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    A Novel Chitosan/Wheat Gluten Biofoam Fabricated by Mixing and Vacuum-dryingManuscript (preprint) (Other academic)
  • 18.
    Chen, Fei
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Gällstedt, Mikael
    Olsson, Richard
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Gedde, Ulf
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Unusual Effects of Monocarboxylic Acids on The Structure and on The Transport and Mechanical Properties of Chitosan Films2015In: Carbohydrate Polymers, ISSN 0144-8617, E-ISSN 1879-1344, Vol. 132, p. 419-429Article in journal (Refereed)
    Abstract [en]

    The purpose of this study was to study the transport of monocarboxylic acids in chitosan films, since this is important for understanding and predicting the drying kinetics of chitosan from aqueous solutions. Despite the wealth of data on chitosan films prepared from aqueous monocarboxylic acid solutions, this transport has not been reported. Chitosan films were exposed to formic, acetic, propionic and butyric acid vapours, it was found that the rate of uptake decreased with increasing molecular size. The equilibration time was unexpectedly long, especially for propionic and butyric acid, nine months. A clear two-stage uptake curve was observed for propionic acid. Evidently, the rate of uptake was determined by acid-induced changes in the material. X-ray diffraction and infrared spectroscopy indicated that the structure of the chitosan acetate and buffered chitosan films changed during exposure to acid and during the subsequent drying. The dried films previously exposed to the acid showed less crystalline features than the original material and a novel repeating structure possibly involving acid molecules. The molar mass of the chitosan decreased on exposure to acid but tensile tests revealed that the films were always ductile. The films exposed to acid vapour (propionic and butyric acid) for the longest period of time were insoluble in the size-exclusion chromatography eluent, and they were also the most ductile/extensible of all samples studied.

  • 19.
    Chen, Fei
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Monnier, Xavier
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Gällstedt, Mikael
    Innventia, Sweden.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hedenqvist, Mikael S.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Wheat gluten/chitosan blends: A new biobased material2014In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 60, p. 186-197Article in journal (Refereed)
    Abstract [en]

    Wheat gluten and chitosan are renewable materials that suffer from some poor properties that limit their use as a potential replacement of petroleum-based polymers. However, polymer blends based on wheat gluten and chitosan surprisingly reduced these shortcomings. Films were cast from acidic aqueous or water/ethanol solutions of wheat gluten and chitosan. Wheat gluten was the discontinuous phase in the 30-70 wt.% wheat gluten interval investigated. The most homogeneous films were obtained when reducing agents were used (alone or together with urea or glycerol). They consisted mainly of 1-2 mu m wheat gluten particles uniformly distributed in the continuous chitosan phase. Slightly smaller particles were also observed in the water/ethanol solvent system, but together with significantly larger particles (as large as 200 mu m). Both small and large particles were observed, albeit in different sizes and contents, when surfactants (both with and without a reducing agent) or urea (without a reducing agent) were used. The particles were often elongated, and preferably along the film, the most extreme case being observed when the glyoxal crosslinker was used together with sodium sulfite (reducing agent), showing particles with an average thickness of 0.6 mu m and an aspect ratio of 4.2. This film showed the highest transparency of all the blend films studied. For one of the most promising systems (with sodium sulfite), having good film homogeneity and small particles, the mechanical and moisture solubility/diffusivity properties were studied as a function of chitosan content. The extensibility, toughness and moisture solubility increased with increasing chitosan content, and the moisture diffusivity was highest for the pristine chitosan material. It is noteworthy that the addition of 30 wt.% wheat gluten to chitosan reduced the moisture uptake, while the extensibility/toughness remained unchanged.

  • 20. Chen, Xiangrong
    et al.
    Murdany, Deni
    Liu, Dongming
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Andersson, Mattias
    Gubanski, Stanislaw M.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Suwarno, S.
    AC and DC Pre-stressed Electrical Trees in LDPE and its Aluminum Oxide Nanocomposites2016In: IEEE transactions on dielectrics and electrical insulation, ISSN 1070-9878, E-ISSN 1558-4135, Vol. 23, no 3, p. 1506-1514Article in journal (Refereed)
    Abstract [en]

    Resistance of pure low density polyethylene (LDPE) and its aluminum oxide nanocomposites (up to 3.0 wt%) to degradation by electrical treeing under AC stress and DC pre-stress is analyzed. The experiments were carried out on wire-plane electrode specimens before and after exposure to thermal and DC electro-thermal ageing at 80 degrees C. The obtained results showed enhanced resistance of the nanocomposites to electrical tree inception under AC stress and the tree inception voltage (TIV) increased with nanoparticles content. It has been shown that there was an improved partial discharge (PD) resistance in the nanocomposites compared to the unfilled LDPE. The results also showed that the AC TIV in the nanocomposites consistently increased with the ageing and especially the DC electro-thermally aged specimens had about 30% higher the AC TIV as compared to the unaged material. This effect is attributed to significantly reduced mobility of charge carriers in the nanocomposites. The DC pre-stressed electrical trees generated in the investigated materials were of filamentary-branch structure and the branch channels content increases with the addition of nanoparticles. The mean tree number of the DC prestressed electrical trees decreased in the LDPE and its nanocomposites while the mean maximum tree length increased with the ageing treatments. It is postulated that material recrystallization and a very high electric field level on the wire electrode during the DC pre-stressed electrical tree test are the main reasons for the observed effects.

  • 21. Cornelio, R. B.
    et al.
    Kopperud, H. M.
    Haasum, Johan
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Örtengren, U.
    Influence of different mould materials on the degree of conversion of dental composite resins2012In: Brazilian Journal of Oral Sciences, ISSN 1677-3217, E-ISSN 1677-3225, Vol. 11, no 4, p. 469-474Article in journal (Refereed)
    Abstract [en]

    Aim: In this study, the degree of conversion (DC) was analyzed on the surfaces of dental composite resins cured in different mould materials with different irradiation times. Methods: Samples of three composite resins (Grandio®, Grandio Flow® [thickness = 2 mm; 4 mm; Ø = 5 mm] irradiated for 10 s, 20 s and 40 s and an experimental composite (EXPM) [thickness = 6 mm; Ø = 5 mm] irradiated for 40 s) were cured in moulds made of polytetrafluorethylene (PTFE), high-density polyethylene (HDPE) and stainless steel (SS). The DC was analyzed by FT-Raman spectroscopy. Results: The DC was significantly lower for the 2-mm-thick samples of Grandio® cured with 20 s in the SS mould than in the PTFE mould. The same trend was found for the 4-mm- thick samples of Grandio Flow® cured with 40 s. The main difference of the DC between Grandio® and Grandio Flow® occurred when 10 s irradiation was used, independently of the mould material and thickness of the samples. The analysis of the DC on the sites around the samples of EXPM showed no significant difference from those at the bottom when cured in each mould material with 40 s irradiation. Conclusions: The DC was not affected by the mould material, instead, the resin formulation and the irradiation times were the main factors affecting the degree of conversion.

  • 22. Cornelio, Roberto Belloti
    et al.
    Wikant, Aksel
    Mjosund, Hanne
    Kopperud, Hilde Molvig
    Haasum, Johan
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Gedde, Ulf
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Ortengren, Ulf Thore
    The influence of bis-EMA vs bis GMA on the degree of conversion and water susceptibility of experimental composite materials2014In: Acta Odontologica Scandinavica, ISSN 0001-6357, E-ISSN 1502-3850, Vol. 72, no 6, p. 440-447Article in journal (Refereed)
    Abstract [en]

    Objective. The aim of this work was to assess the influence of the bis-EMA content on the degree of conversion (DC) and its effect on the water sorption and solubility. Materials and methods. In a polytetrafluorethylene (PTFE) mould, 30 samples (O = 5 mm, height = 2 mm) of four experimental dental composite resins were cured for 10 s, 20 s and 40 s. The DC was analysed by Fourier Transform (FT)-Raman spectroscopy. To analyse sorption and solubility, six samples (O = 15 mm and thickness = 1 mm) of each composite (n = 72) were stored in water at 37 degrees C for different storage periods: 24 h, 7 days and 30 days. Results. When cured for 20 or 40 s the DC increased with the increasing content of bis-EMA. However, the presence of 15 wt% of bis-GMA did not affect the DC, except when cured with 10 s irradiation time. This study also found a correlation between the content of bis-EMA and the reduced values for sorption and solubility, for all storage times used, when the materials were cured with 20 s. Conclusions. The DC of mixtures with higher content of bis-EMA is affected by the presence of bis-GMA at lower energy density delivered from the curing device, suggesting that the restrictions caused by the presence of hydrogen bonds is dependent of the irradiation time used.

  • 23.
    Ekelund, Maria
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Azhdar, Bruska
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Evaporative loss kinetics of di(2-ethylhexyl)phtalate (DEHP) from pristine DEHP and plasticized PVCManuscript (preprint) (Other academic)
  • 24.
    Ekelund, Maria
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Azhdar, Bruska
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Evaporative loss kinetics of di(2-ethylhexyl)phthalate (DEHP) from pristine DEHP and plasticized PVC2010In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 95, no 9, p. 1789-1793Article in journal (Refereed)
    Abstract [en]

    The migration of di(2-ethylhexyl)phthalate (DEHP) from poly(vinyl chloride) (PVC) to a surrounding gas phase at temperatures below 120 degrees C kinetically is controlled by evaporation. The effects on the DEHP loss rate of nitrogen flow rate, relative humidity and degradation of the plasticizer at 100 degrees C was assessed. The sample mass decreased linearly with time for both pristine DEHP and plasticized PVC at comparable rates, suggesting that a thin film of DEHP was present on the jacketing insulation during desorption. The latter hypothesis was supported by infrared spectroscopy and by the fact that DEHP is an amphiphilic molecule that will tend to aggregate at the surface with the hydrophobic 2-ethylhexyl units at the air interface. The effect on the migration rate of moisture present in the gas phase was negligible. The DEHP loss rate increased in a retarding non-linear fashion with increasing gas flow rate. In one of the experiments, DEHP was accidently degraded as revealed by discoloration, the presence of low molar mass degradation products (liquid chromatography) containing additional carbonyl groups (infrared spectroscopy) and an increase in the evaporation rate at temperatures between 100 and 130 degrees C. (C) 2010 Elsevier Ltd. All rights reserved.

  • 25.
    Ekelund, Maria
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Azhdar, Bruska
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hedenqvist, Mikael S
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Gedde, Ulf W
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Long-term performance of poly(vinyl chloride) cables, Part 2: Migration of plasticizer2008In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 93, no 9, p. 1704-1710Article in journal (Refereed)
    Abstract [en]

    Cable samples with plasticized poly(vinyl chloride) insulations were aged in air at temperatures between 80 and 155 degrees C. The concentrations of the plasticizer (di-(2-ethylhexyl) phthalate, DEHP) in the insulations of the aged cables were determined by extraction of samples in tetrahydrofuran followed by analysis of the extract by liquid chromatography. The plasticizer concentration data for different ageing times were analysed by numerical methods, fitting Fick's second law with a concentration-dependent diffusivity. The analysis showed that the transport of the plasticizer to the surrounding air phase was controlled by diffusion at 120 and 155 degrees C with an activation energy of 89 kJ mol(-1). The evaporation of the plasticizer from the outer boundary was rate controlling at lower temperatures (<= 100 degrees C), The rate of evaporation was initially constant and independent of the plasticizer concentration at both 80 and 100 degrees C. The activation energy for the initial DEHP loss rate from PVC at these temperatures was the same as that obtained for evaporation of pure DEHP on a glass plate at 60-100 degrees C measured by thermogravimetry, 98 2 kJ mol-1. Furthermore, the evaporation rate of pure DEHP on a glass plate was also of the same order of magnitude as the rate of plasticizer loss from the cable insulation. Extrapolation of the plasticizer loss rate data (from the cable at 80 degrees C and from pure liquid DEHP at temperatures between 60 and 100 IQ to 25 degrees C predicted a maximum loss of plasticizer of 1% over 25 years. This is in accordance with earlier presented data and with the data presented in this report.

  • 26.
    Ekelund, Maria
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Edin, Hans
    KTH, School of Electrical Engineering (EES), Electromagnetic Engineering.
    Gedde, Ulf W
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Long-term performance of poly(vinyl chloride) cables. Part 1: Mechanical and electrical performances2007In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 92, no 4, p. 617-629Article in journal (Refereed)
    Abstract [en]

    Cables insulated with plasticized poly(vinyl chloride) were aged in air at temperatures between 80 degrees C and 180 degrees C and their conditions were assessed by indenter modulus measurements, tensile testing, infrared (IR) spectroscopy and differential scanning calorimetry (DSC). Electrical testing of oven-aged cable samples was performed in order to relate the electrical functionality during a high-energy line break (HELB) to the mechanical properties and to establish a lifetime criterion. The mechanical data taken at room temperature after ageing could be superimposed with regard to ageing time and temperature. The ageing-temperature shift factor showed an Arrhenius temperature dependence. The jacketing material showed an immediate increase in stiffness (indenter modulus and Young's modulus) and a decrease in the strain at break on ageing; these changes were dominated by loss of plasticizer by migration which was confirmed by IR spectroscopy and DSC. The core insulation showed smaller changes in these mechanical parameters; the loss of plasticizer by migration was greatly retarded by the closed environment, according to data obtained by IR spectroscopy and DSC, and the changes in the mechanical parameters were due to chemical degradation (dehydrochlorination). A comparison of data obtained from this study and data from other studies indicates that extrapolation of data for the jacketing insulation can be performed according to the Arrhenius equation even down to service temperatures (20-50 degrees C). The low-temperature deterioration of the jacketing is, according to this scheme, dominated by loss of plasticizer by migration.

  • 27.
    Ekelund, Maria
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Fantoni, P. F.
    Gedde, Ulf
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Thermal ageing assessment of EPDM-chlorosulfonated polyethylene insulated cables using line resonance analysis (LIRA)2011In: Polymer testing, ISSN 0142-9418, E-ISSN 1873-2348, Vol. 30, no 1, p. 86-93Article in journal (Refereed)
    Abstract [en]

    Two cables with chlorosulfonated polyethylene jackets and EPDM core insulations, but having different designs and geometries, were aged at 140 degrees C for different periods of time mimicking ageing at 50 degrees C for an exposure time of more than one hundred years. The cable samples were aged in dry air and dry nitrogen. The cable samples were studied with indenter modulus measurements, tensile tests, infrared spectroscopy and line resonance analysis (LIRA). The main question was whether universal correlations could be established between the two classical methods (indenter and tensile testing) and LIRA. The global ageing indicator (CBAC2) obtained by LIRA showed good correlation with the indenter modulus of the jacketing and with the mechanical properties of the core insulation. Almost universal CBAC2 values were obtained for samples reaching a critical state; the latter being defined according to a criterion based on LOCA test data. Infrared spectroscopy showed that the core insulation degraded by an essentially oxygen-free mechanism, with a gradual increase in the concentration of vinyl and vinylene groups. (C) 2010 Elsevier Ltd. All rights reserved.

  • 28.
    Ekelund, Maria
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Fantoni, Paolo F.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Thermal ageing assassment of EPDM/CSPE-insulated cables using advanced condition-monitoring techniques.Manuscript (preprint) (Other academic)
  • 29.
    Ekelund, Maria
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Lifetime prediction : different strategies by example2009In: POLYMER DEGRADATION AND PERFORMANCE / [ed] Celina MC; Wiggins JS; Billingham NC, 2009, Vol. 1004, p. 159-169Conference paper (Refereed)
    Abstract [en]

    Two different approaches for lifetime prediction are presented. The underlying lifetime limiting processes have been identified in two cases. Mathematical expressions of chemical/physical relevance were used for the lifetime predictions for PE hot-water pipes and cables insulated with plasticized PVC. Accelerated testing, extrapolation and validation of the extrapolation by assessment of the remaining lifetime of objects aged during service conditions for 25 years were successfully applied to cables insulated with chlorosulfonated polyethylene. Polyolefin pipes exposed to chlorinated water showed a very complex deterioration scenario and it was only possible to find a method suitable for predicting the time for the depletion of the stabilizer system.

  • 30. Fateh-Alavi, K.
    et al.
    Gallstedt, M.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    The effect of antioxidants on the surface oxidation and surface cracking of crosslinked polydimethylsiloxane2001In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 74, no 1, p. 49-57Article in journal (Refereed)
    Abstract [en]

    Crosslinked polydimethylsiloxanes with three different chain-breaking antioxidants (Irganox 1076, Irganox 565 and Tinuvin 770) were exposed to air plasma (GHz), and the surface structures of the exposed samples were assessed by contact angle measurements, X-ray photoelectron spectroscopy, optical and scanning electron microscopy, and surface profilometry before and after uniaxial stretching. It was found that samples containing antioxidants oxidized more slowly than the reference sample with no antioxidant. Higher doses of air plasma were required to form a brittle silica-like layer in the samples with antioxidant than in the reference sample with no antioxidant. Tinuvin 770 showed the strongest antioxidative effect whereas Irganox 1076 and Irganox 565 were similar in efficiency.

  • 31. Fateh-Alavi, K.
    et al.
    Nunez, M. E.
    Karlsson, Sigbritt
    KTH, Superseded Departments, Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    The effect of stabilizer concentration on the air-plasma-induced surface oxidation of crosslinked polydimethylsiloxane2002In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 78, no 1, p. 17-25Article in journal (Refereed)
    Abstract [en]

    The concentrations of three stabilizers-a hindered phenol (Irganox 1076), a hindered amine light stabilizer (Tinuvin 770) and a bifunctional stabilizer with chain-breaking hindered phenol and secondary amine and hydroperoxide-decomposing sulphide moieties (Irganox 565)-in crosslinked polydimethylsiloxane were varied using swelling solutions of the stabilizers at different concentrations. The concentration of the stabilizer in the rubber was assessed by UV-Vis spectroscopy of Soxhlet and microwave assisted extracts. Irganox 1076 and Tinuvin 770 were soluble in polydimethylsiloxane to at least 0.2-0.3 wt.%, whereas the solubility of Irganox 565 was considerably lower. The samples were exposed to GHz air plasma and the surface structures of the exposed samples were studied by X-ray photoelectron spectroscopy, and by optical and scanning electron microscopy after uniaxial stretching. The plasma exposure time required for the formation of an oxidised glassy layer increased in a linear fashion with increasing stabilizer concentration, suggesting that the consumption rate was constant in time during the plasma exposure. Tinuvin 770 showed the strongest overall protecting effect whereas Irganox 565 showed the strongest protecting effect per mass fraction of stabilizer. Irganox 1076 was of moderate efficiency. The results suggest that efficient protection towards air plasma is achieved with hindered amine stabilizers or with stabilizers combining chain-breaking and hydroperoxide-decomposing functions. Differential scanning calorimetry showed that Tinuvin 770 and Irganox 565 protected polydimethylsiloxane against thermal oxidation at elevated temperatures. The chemical consumption of these stabilizers followed basically the classical scheme with zero-order kinetics and a rate constant obeying the Arrhenius law.

  • 32.
    Fateh-Alavi, Kamyar
    et al.
    KTH, Superseded Departments, Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Effect of stabilizers on surface oxidation of silicone rubber by corona discharge2004In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 84, no 3, p. 469-474Article in journal (Refereed)
    Abstract [en]

    Crosslinked polydimethylsiloxane (PDMS) containing Irganox(R) 1076, Tinuvin(R) 770 or lrganox(R) 565, prepared by swelling PDMS in a solution of one of these stabilizers in n-hexane, was exposed to a corona discharge and the corona exposure time (tau(crit)) to form a brittle, silica-like layer was determined by optical microscopy. The critical corona exposure time showed a linear increase with increasing stabilizer concentration; Tinuvin 770 showed the highest efficiency and Irganox 1076 the lowest. The increase in tau(crit) on corona exposure of the stabilized samples with reference to the value for unstabilized PDMS was similar to that reported earlier for air plasma exposed samples. The efficiency of the stabilizers towards corona-induced surface oxidation of PDMS was also confirmed by X-ray photoelectron spectroscopy.

  • 33.
    Fateh-Alavi, Kamyar
    et al.
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Karlsson, Sigbritt
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    A rapid microwave-assisted solvent extraction method for assessment of stabilizer concentration in crosslinked polydimethylsiloxane2004In: Journal of Applied Polymer Science, ISSN 0021-8995, E-ISSN 1097-4628, Vol. 93, no 5, p. 2185-2192Article in journal (Refereed)
    Abstract [en]

    Crosslinked polyclimethylsiloxanes were prepared containing 0.05 to 0.2 wt % of either a phenolic antioxidant (Irganox(R) 1010) or a hindered amine stabilizer (Tinuvin(R) 144). The stabilizer concentration was assessed by HPLC and UV-Vis spectroscopy of Soxhlet and microwave-assisted solvent extracts. Almost complete recovery of stabilizer was achieved with Soxhlet extraction. High stabilizer recovery was achieved when acetone was used as the solvent in the microwave-assisted extraction. HPLC was shown to be an efficient method for determining the concentration of Irganox 1010. For Tinuvin 144 the selectivity of both UV-Vis spectroscopy and HPLC was poor, leading to imprecise evaluation of the antioxidant concentration. The loss of stabilizer by migration from polymer to hot water (75 and 95degreesC) was monitored for the systems stabilized with Irganox 1010 and the diffusion coefficient of the antioxidant in the polymer was determined.

  • 34. Flodberg, G.
    et al.
    Axelson-Larsson, L.
    Hedenqvist, Mikael S.
    KTH, Superseded Departments, Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Liquid Crystalline Polymer Pouches for Local Anaesthetic Emulsion2001In: Packaging technology & science, ISSN 0894-3214, E-ISSN 1099-1522, Vol. 14, no 4, p. 159-170Article in journal (Refereed)
    Abstract [en]

    In order to enhance the long-term properties of a high-pH local anaesthetic drug, emulsion tests were conducted where the emulsion was stored in pouches made of a compression moulded high-barrier liquid-crystalline polymer, Vectra A950. The oxygen permeability of the pouch materia I was too low to be detected at 23 degreesC and 0% relative humidity with the instrument used. The water vapour transmission rate was 0.135 (g.mm/m(2).day) at 38 degreesC and 100% relative humidity. The emulsion, containing prilocain and lidocain as active substances, was stored in pouches which were sealed by the thermal impulse technique at 260 degreesC for 1.08 s. It was possible to obtain good quality films and good quality seals by optimization of the compression moulding and sealing operations. The concentrations of prilocain and lidocain in the emulsion were studied for 14 weeks at two different temperatures, 40 degreesC and 60 degreesC, and at 100% relative humidity. The decrease in concentration was higher for prilocain (5.4-8.3%) than for lidocain (3.4-3.6%). The loss of the substances from the emulsion was due mainly to adsorption onto the polar surface of the liquid crystalline polymer.

  • 35. Flodberg, G.
    et al.
    Hedenqvist, Mikael S.
    KTH, Superseded Departments, Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Barrier properties of injection molded blends of liquid crystalline polyesters (Vectra) and high-density polyethylene2003In: Polymer Engineering and Science, ISSN 0032-3888, E-ISSN 1548-2634, Vol. 43, no 5, p. 1044-1057Article in journal (Refereed)
    Abstract [en]

    Blends of an extrusion-grade high-density polyethylene and two liquid crystalline copolyesters (LCP; Vectra A950 and Vectra RD501) were prepared by melt mixing and injection molding, and the. morphologies and oxygen permeabilities of the blends were assessed. Scanning electron microscopy revealed that the LCP was present in the blends as mixed oriented bands and small spheres at low LCP contents (4-9 vol%), Whereas blends with more than 18 vol% LCP showed LCP lamellae of macroscopic lateral size (mm). Scanning electron microscopy revealed a two-dimensional continuity of the LCP domains in the disc plane due to radial shear deformation and circumferential stretching of the melt leaving the central gate of the disc-shaped cavity. The oxygen permeability, diffusivity and solubility decreased with increasing LCP content of the blends. The decrease in permeability with respect to polyethylene was significant (46%-55%) already at 9 vol% LCP. At 27 vol% LCP, the decrease with respect to polyethylene, was 92% for the Vectra A950 blend and 98% for the Vectra RD501 blend. These blends showed a greater decrease in diffusivity (86%-92%) than in solubility (39%-76%) with respect to polyethylene, which showed the very pronounced effect of the LCP lamellae on the geometrical impedance factor. Microvoids were present in all the blends despite the use of a very high injection pressure (180 MPa) but their impact on the oxygen permeability was negligible for the Vectra. RD501 blends and relatively small for the Vectra A950 blends.

  • 36. Flodberg, G.
    et al.
    Hellman, A.
    Hedenqvist, Mikael S.
    KTH, Superseded Departments, Polymer Technology.
    Sadiku, E. R.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Barrier properties of blends based on liquid crystalline polymers and polyethylene2000In: Polymer Engineering and Science, ISSN 0032-3888, E-ISSN 1548-2634, Vol. 40, no 9, p. 1969-1978Article in journal (Refereed)
    Abstract [en]

    Blends of an extrusion-grade polyethylene and two different liquid crystalline polymers of Vectra type were prepared by melt mixing using poly(ethylene-co-methacrylic acid) as compatibilizer. Oxygen and water vapor permeability, transparency and welding strength of compression molded and film blown specimens were studied. The compression molded blends showed gas permeabilities conforming to the Maxwell equation assuming low permeability liquid crystalline polymer spheres in a high permeability polyethylene matrix One of the liquid crystalline polymers with suitable rheological properties formed a more continuous phase in the film blown blends and a substantial decrease in oxygen and water vapor permeability was observed in these blends. The compression molded blends with 50% liquid crystalline polymer and some of blow molded blends showed very high gas permeabilities. It is believed that voids forming continuous paths through the structure were present in these samples. The blends showed significantly higher opacity than pure polyethylene.

  • 37. Flodberg, G.
    et al.
    Hojvall, L.
    Hedenqvist, Mikael S.
    KTH, Superseded Departments, Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Migration of monomers from liquid crystalline poly(p-hydroxybenzoic acid-co-2-hydroxy-6-naphthoic acid)2002In: Food Additives and Contaminants, ISSN 0265-203X, E-ISSN 1464-5122, Vol. 19, no 5, p. 492-501Article in journal (Refereed)
    Abstract [en]

    Liquid-crystalline co-polyesters (e.g. a random co-polyester based on p-hydroxybenzoic acid (HBA) and 2-hydroxy-6-naphthoic acid (HNA) known as Vectra A950) offer good barrier properties, but for food-contact use require overall and specific migration testing. For Vectra A950 films, the highest overall migration level obtained was 2.3 mg kg(-1) in olive oil (10 days at 40degrees C) well below the EC limit of 60 mg kg(-1). The highest specific migration for p-hydroxybenzoic acid was 15.2 mug dm(-2) in olive oil (2 h at 175degreesC). For 2-hydroxy-6-naphthoic acid, the highest value obtained was 4.3 mug dm(-2) in 10% ethanol (4 h at 100degrees C), although it was not on the EC positive and cannot yet be used for food-contact materials. At conditions considered as severe, the estimated daily intake for p-hydroxybenzoic acid was calculated as 11.9 mug/person day(-1) and for 2-hydroxy-6-naphthoic acid it was 5.3 mug/person day(-1). The results exceed the threshold of regulation of 1.5 mug/person day(-1).

  • 38.
    Gedde, Ulf
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Hjertberg, Thomas
    Borealis.
    Costa, Francis
    Borealis/Linz.
    Oderkerk, Jeroen
    Borealis.
    Polyolefin composition with increased resistance against degradation caused by chlorine dioxide2011Patent (Other (popular science, discussion, etc.))
    Abstract [en]

    The present invention relates to a polyolefin composition with increased resistance to degradation caused by ClO2-containing water and to an article made of such a polyolefin composition. The polyolefin composition comprises a polyolefin base resin (A), at least one antioxidant (B) having an initial oxygen induction time (OIT190°C) of more than 35 min., determined according to the OIT190°C test described herein and having a slope of the curve, when OIT190°C, in minutes, is recorded as a function of exposure time, in minutes, in a chlorine dioxide degradation test as described herein, of at least -0.07, and c) at least one antioxidant (C) having an initial oxygen induction time (OIT190°C) of not more than 35 min., determined according to the OIT190°C test described herein and having a slope of the curve, when OIT190°C, in minutes, is recorded as a function of exposure time, in minutes, in a chlorine dioxide degradation test as described herein, of less than -0.07, wherein said polyolefin composition shows a resistance against water containing 10 ppm chlorine dioxide at 70 °C and a pH of 6.8 ± 0.1 of at least 450 min., expressed as the time to reach 50% of the initial oxygen induction time at 210 °C (OIT(210°C),50%), determined according to the chlorine dioxide degradation test as described herein. The present invention further relates to the use of the polyolefin composition for the production of an article, e.g. a pipe, a fitting or a storage container and to the use of the polyolefin composition for increasing the resistance of an article against degradation caused by contact with ClO2-containing water.

  • 39.
    Gedde, Ulf W
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
    Untitled2016In: Polymer testing, ISSN 0142-9418, E-ISSN 1873-2348, Vol. 55, p. A2-A2Article in journal (Other academic)
  • 40. Gustavsson, T. G.
    et al.
    Gubanski, S. M.
    Hillborg, H.
    Karlsson, Sigbritt
    KTH, Superseded Departments, Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Aging of silicone rubber under ac or dc voltages in a coastal environment2001In: IEEE transactions on dielectrics and electrical insulation, ISSN 1070-9878, E-ISSN 1558-4135, Vol. 8, no 6, p. 1029-1039Article in journal (Refereed)
    Abstract [en]

    Material samples of silicone rubber with known differences in their composition, i.e. different filler content and extra silicone oil added, have been aged at the Anneberg field station on the west coast of Sweden. ac or dc voltage supplied to cylindrical samples at stress levels of 50 or 100 V/mm. The work includes laboratory examination of material changes together with on-site, visual observations and leakage current measurements. Material samplings for the laboratory tests were made after 18 months of electrical aging, which went on for one more year in order to gather further information on the long-term electrical performance of the material. The dominant aging factor was the level of the applied stress, independent of ac or dc voltage. The dc stressed samples showed a higher leakage current and exhibited larger surface degradation compared with samples exposed to ac voltage. The material parameter, an addition of extra silicone oil, initially lead to an increase in adhesion of pollutants, whereas the overall performance was improved by the higher suppression of the leakage current related to oligomer diffusion. Samples with lower level of alumina trihydrate (ATH) exhibited a delayed onset of degradation, but once damaged they degraded more rapidly than the specimens with a higher ATH content. Infrared spectroscopy showed that the ATH was completely consumed at the eroded surface regions. The aging of the surfaces was further assessed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The low molar mass siloxanes present in the pollution layer were extracted and analyzed by size exclusion chromatography and gas chromatography-mass spectroscopy. The results indicated that the main degradation factor was thermal depolymerization activated by electrical discharges. Oxidative crosslinking of the silicone rubber, usually attributed to surface close corona discharges, appeared to have played a minor role.

  • 41. Hassinen, J.
    et al.
    Lundbäck, Marie
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Ifwarson, M.
    Gedde, Ulf
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Deterioration of polyethylene pipes exposed to chlorinated water2004In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 84, no 2, p. 261-267Article in journal (Refereed)
    Abstract [en]

    Pipes of high-density polyethylene were exposed to chlorinated water at elevated temperatures. The materials were stabilised with hindered phenols and phosphites. Oxidation induction times measured by DSC showed that the stabilising system was rapidly chemically consumed by the action of chlorinated water. Size exclusion chromatography and DSC showed extensive polymer degradation strictly confined to the immediate surface of the unprotected inner wall material and to the amorphous phase of the semicrystalline polymer. The rate of growth of the layer of highly degraded polymer was constant. It is obvious from the data that the species responsible for the loss of antioxidant are soluble in the polymer but not very reactive with the polymer itself. The species responsible for polymer degradation, on the other hand, are very reactive with the polymer and/or have a very low solubility in the polymer.

  • 42.
    Hedenqvist, Mikael S.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Backman, A.
    Gallstedt, M.
    Boyd, R. H.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Morphology and diffusion properties of whey/montmorillonite nanocomposites2006In: Composites Science And Technology, ISSN 0266-3538, E-ISSN 1879-1050, Vol. 66, no 13, p. 2350-2359Article in journal (Refereed)
    Abstract [en]

    The diffusion of methanol in solution-cast whey-protein-isolate/poly(vinylidene pyrrolidone)-coated montmorillonite composite films was studied. The filler content was 0-4.8 vol%. Desorption experiments on samples saturated in methanol were conducted in a nitrogen-purged chamber at 294 K or in a thermogravimeter at 333, 348 and 363 K. The desorption curves were fitted using a two-phase diffusion model; where diffusion occurred first in the rubbery and later in the glassy state. A free volume model was used to analyze desorption at 363 K which occurred only within the rubbery phase and it enabled the geometrical impedance factor and free volume constraints from the nanoparticles to be assessed. Transmission electron microscopy showed a partial exfoliation of the nanoparticles. The geometrical impedance factor increased markedly with increasing filler content in accordance with the high aspect ratio of the nanoparticle aggregates. Transmission electron microscopy, in combination with model calculations, revealed that the clay sheets were oriented preferentially in the plane of the film which was an important factor underlying the high geometrical impedance factor obtained for the nanocomposites. A small but significant reduction in the fractional free volume of the polymer matrix was observed for the rubbery polymer in the presence of montmorillonite.

  • 43.
    Hedenqvist, Mikael S.
    et al.
    KTH, Superseded Departments, Polymer Technology.
    Krook, M.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Two-stage sorption in rubbery semicrystalline polymers: transport of primary alcohols in polyesteramide2002In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 43, no 10, p. 3061-3068Article in journal (Refereed)
    Abstract [en]

    This paper deals with the two-stage sorption of methanol, 1-propanol and I-hexanol in a rubbery semicrystalline polyesteramide. This is the first time two-stage sorption is reported for a semicrystalline rubbery polymer. Mass uptake, specimen geometry and surface concentration were measured independently. The two-stage sorption curve describes two overlapping processes; a very rapid diffusion (mode 1) superimposed onto a normal s-shaped sorption curve (mode 2). Mode I swelling was uni-dimensional and mode 2 swelling was initially uni-dimensional and later three-dimensional. It was possible to model the sorption curves by assuming time-dependent solute-surface-concentration conditions, similar to those used to describe simple s-shaped sorption. The obtained time dependence, characterised by a single relaxation time, agreed with experimental values of the surface concentration obtained by infrared spectroscopy. The relaxation time increased exponentially with increasing size of the diffusing alcohol molecule. The solubility of the alcohols in the polymer increased with increasing hydroxyl-group density. The diffusivity of alcohol decreased nonlinearly with increasing length of the molecule, size effects being less important for larger solutes.

  • 44.
    Hedenqvist, Mikael S.
    et al.
    KTH, Superseded Departments, Polymer Technology.
    Yousefi, Hamid Reza
    KTH, Superseded Departments, Polymer Technology.
    Malmström, Eva
    KTH, Superseded Departments, Polymer Technology.
    Johansson, Mats K. G.
    KTH, Superseded Departments, Polymer Technology.
    Hult, Anders
    KTH, Superseded Departments, Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Trollsas, M.
    Hedrick, J. L.
    Transport properties of hyperbranched and dendrimer-like star polymers2000In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 41, no 5, p. 1827-1840Article in journal (Refereed)
    Abstract [en]

    Moisture transport properties were assessed by sorption and desorption measurements on hydroxyl-functional hyperbranched polyesters based on 2,2-bis(methylol) propionic acid (bis-MPA) as AB(2)-monomer with ethoxylated pentaerythritol. A series of these polymers with different molar masses were studied. For the first time, it is reported that sigmoidal sorption curves were successfully modelled using a time-dependent surface boundary concentration, where the relaxation time was obtained from the mechanical stress relaxation data. The zero concentration diffusivities were very small and comparable with the values of fully amorphous poly(vinyl alcohol). Both the diffusivity data and the stress relaxation data indicated that these materials were plasticized by moisture. Ethylene glycol transport properties were measured on a hexadecanoate(C16)-terminated bis-MPA hyperbranched polymer. The replacement of the hydroxyl groups with C16 paraffin tails resulted in an increase in solute diffusivity despite the fact that these polymers became semicrystalline. The shape of the desorption curves indicated that continuous micropores were present and facilitated mass transport. The moisture transport properties were also measured on a series of semicrystalline dendrimer-like star poly(epsilon-caprolactone(s)). The low measured densities of these highly crystalline dendrimers confirmed that the porosity, as indicated by the shape of the desorption curves, had to be discontinuous. The porosity in the (C16)-terminated and the poly(epsilon-caprolactone(s)) was impossible to eliminate by applying a high external pressure during crystallization. A collective view of all the results obtained confirm that the transport properties are primarily controlled by the hydroxyl group concentration.

  • 45. Hillborg, H.
    et al.
    Ankner, J. F.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Smith, G. D.
    Yasuda, H. K.
    Wikstrom, K.
    Crosslinked polydimethylsiloxane exposed to oxygen plasma studied by neutron reflectometry and other surface specific techniques2000In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 41, no 18, p. 6851-6863Article in journal (Refereed)
    Abstract [en]

    Spin-coated specimens of crosslinked polydimethylsiloxane (PDMS) exposed to radio-frequency (RF) and microwave (MW) oxygen plasma were studied by specular neutron reflectometry, X-ray photoelectron spectroscopy (XPS), Wilhelmy balance, contact angle measurements, scanning electron microscopy and atomic force microscopy. Neutron reflectometry and XPS showed that the oxygen plasma led to the formation of a smooth (<10 nm), oxidised surface layer with a thickness of 130-160 nm. The oxidised layer contained a mixture of the original polymer and silicon bonded to three or four oxygen atoms (SiOx). The oxidised layer was thinner after longer plasma exposure, indicating a decrease in specific volume due to a conversion of the polymer structure to an inorganic SiOx-rich structure. The formation of the SiOx-containing layer with low segmental mobility was further confirmed by the small hysteresis in the Wilhelmy balance measurements. The similarity in the hydrophobicity recovery kinetics of specimens aged in dry air, dry argon and vacuum and XPS data showed that the hydrophobicity recovery is not due to contamination through adsorption from the atmosphere but due to migration of low molar mass PDMS species to the surface. Scanning electron microscopy also showed the presence of surface cracks in heavily oxidised specimens.

  • 46. Hillborg, H.
    et al.
    Karlsson, Sigbritt
    KTH, Superseded Departments, Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Characterisation of low molar mass siloxanes extracted from crosslinked polydimethylsiloxanes exposed to corona discharges2001In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 42, no 21, p. 8883-8889Article in journal (Refereed)
    Abstract [en]

    Crosslinked polydimethylsiloxanes were exposed to corona discharges in dry air at normal pressure. Short-time solvent extraction and subsequent analysis of the extractables, by gas chromatography, mass spectrometry and size exclusion chromatography showed that, oligomers consisting mainly of cyclics with 4-9 repeating units were formed during corona exposure. The size distribution of the oligomers was independent of the crosslink density and corona exposure time. The amount of oligomers located at the surface increased, with increasing storage time, after the corona exposure in qualitative agreement with the ongoing hydrophobic recovery process. Longer extractions penetrated deeper into the samples, and, in addition to the cyclic oligomers, higher molar mass species (similar to 50,000 g mol(-1) for unexposed samples) were detected. Samples exposed to corona, treated in this way, showed a broadening of the high molar mass peak towards lower molar masses.

  • 47. Hillborg, H.
    et al.
    Sandelin, M.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Hydrophobic recovery of polydimethylsiloxane after exposure to partial discharges as a function of crosslink density2001In: Polymer, ISSN 0032-3861, E-ISSN 1873-2291, Vol. 42, no 17, p. 7349-7362Article in journal (Refereed)
    Abstract [en]

    Polydimethylsiloxanes with different crosslink densities were exposed to corona discharges or GHz air plasma and studied by contact angle measurements, X-ray photoelectron spectroscopy, optical microscopy, scanning electron microscopy and atomic force microscopy. The degree of surface oxidation increased with increasing exposure time with a limiting depth of 100-150 nm. Surface oxidation was faster in more highly crosslinked polymers. Within the oxidised layer, a brittle, microporous silica-like layer with a minimum organic silicone content of 40% gradually developed with increasing exposure time. The strain at which the silica-like layer cracked decreased with increasing dose of corona or air plasma. The hydrophobic recovery following the corona/air plasma exposure occurred at a slow rate by diffusion of oligomers through the microporous but uncracked silica-like layer or at a much higher rate by transport of oligomers through cracks in the silica-like layer.

  • 48. Hoang, A. T.
    et al.
    Pallon, Love
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Liu, Dongming
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Serdyuk, Y. V.
    Gubanski, S. M.
    Gedde, Ulf W.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Charge transport in LDPE nanocomposites part I-experimental approach2016In: Polymers, ISSN 2073-4360, E-ISSN 2073-4360, Vol. 8, no 3, p. 1-19Article in journal (Refereed)
    Abstract [en]

    This work presents results of bulk conductivity and surface potential decay measurements on low-density polyethylene and its nanocomposites filled with uncoated MgO and Al2O3, with the aim to highlight the effect of the nanofillers on charge transport processes. Material samples at various filler contents, up to 9 wt %, were prepared in the form of thin films. The performed measurements show a significant impact of the nanofillers on reduction of material's direct current (dc) conductivity. The investigations thus focused on the nanocomposites having the lowest dc conductivity. Various mechanisms of charge generation and transport in solids, including space charge limited current, Poole-Frenkel effect and Schottky injection, were utilized for examining the experimental results. The mobilities of charge carriers were deduced from the measured surface potential decay characteristics and were found to be at least two times lower for the nanocomposites. The temperature dependencies of the mobilities were compared for different materials.

  • 49. Jansson, S. E. A.
    et al.
    Edsman, C. J.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Hedenqvist, Mikael S.
    KTH, Superseded Departments, Polymer Technology.
    Packaging materials for fermented milk: Effects of material crystallinity and polarity on food quality2001In: Packaging technology & science, ISSN 0894-3214, E-ISSN 1099-1522, Vol. 14, no 3, p. 119-127Article in journal (Refereed)
    Abstract [en]

    The ability of a packaging material to protect the food product and extend its shelf-life depends on several material properties. In this work the effects of material crystallinity and polarity on the quality of fermented milk were studied. The fermented milk is a high-quality Swedish product, similar to yoghurt. The quality of the food product was determined as a function of storage time by containing the liquid in pouches of different materials. The material crystallinity was varied by using very low-density polyethylene, high-density polyethylene and aluminium laminate as packaging materials. Aluminium was used on account of its '100%' gas-tightness. The polarity was varied by comparing an aliphatic polyketone with polyethylene of similar crystallinity. The carbon dioxide (CO2) and oxygen (O-2) contents in the headspace of the pouches were determined. The food quality was determined by measuring whey syneresis, viscosity and the content of desired Bifidobacteria, as well as of undesired yeast and mould. A trained taste panel determined the degree of acidity and of the sparkling taste. It was found that the content of CO2 increased and that of O-2 decreased in the pouches with increasing degree of crystallinity and increasing polarity. The sparkling taste of fermented milk was a clear function of the headspace CO2 content. The data presented here could thus be used to 'design' a package for a desired sparkling taste of the fermented milk by selecting a certain material crystallinity. Whey syneresis, viscosity and content of Bifidobacteria were found to be independent of pouch material. While the degree of whey syneresis and the viscosity increased with increasing storage time, the content of Bifidobacteria slowly decreased. The content of yeast and mould in the liquid was below the existing limit values for foodstuffs. The degrees of acidity and sparkling taste were highest for the liquids contained in aluminium and polyketone pouches, although the differences in acidulous taste between the various pouch materials were small.

  • 50. Jansson, S. E. A.
    et al.
    Gallet, G.
    Hefti, T.
    Karlsson, Sigbritt
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Gedde, Ulf W.
    KTH, Superseded Departments, Polymer Technology.
    Hedenqvist, Mikael S.
    KTH, Superseded Departments, Polymer Technology.
    Packaging materials for fermented milk Part 2: Solute-induced changes and effects of material polarity and thickness on food quality2002In: Packaging technology & science, ISSN 0894-3214, E-ISSN 1099-1522, Vol. 15, no 6, p. 287-300Article in journal (Refereed)
    Abstract [en]

    This work is a continuation of the application of a developed methodology for the selection of packaging material for a specific food product, in this case the 'demanding' food product. fermented milk. The effects of different packaging material parameters on the quality of fermented milk were studied. Food quality after storage was determined as a function of material polarity and pouch thickness by storing the liquid in pouches of different materials. The material polarity was varied by using laminates with polyethylene, poly(ethylene-co-vinyl alcohol) with two different ethylene contents and an aliphatic polyketone. The effects of pouch thickness were studied using high-density polyethylene films of different thicknesses between 25 mum and 200 mum. The interactions between the milk product and the pouch material were analysed by oxygen and water permeability, gas chromatography-mass spectrometry and tensile testing. The CO2 and O-2 contents in the headspace of the pouches were determined. The food quality was determined by measuring whey syneresis and the contents of Bifidobacteria, Enterobacteriaceae, yeast and mould. A trained taste panel determined the sensory properties. The content of CO2, and consequently the sparkling taste, increased with increasing polarity and/or pouch thickness. The CO2 content was affected more easily by changes in material polarity than by changes in pouch thickness. The increase in whey syneresis and the decrease in Bifidobacteria content with time were independent Of material polarity and pouch thickness. The contents Of Enterobacteriaceae, yeast and mould in the liquid were always below existing limits for foodstuffs. A newly developed method was used by which the CO2 and 02 permeabilities of the pouch/packaging could be estimated, using the kinetics of the gas composition in the pouch headspace. Permeability values, as estimated by the method, revealed that the CO2 production and the O-2 consumption rates of the fermented milk were dependent on the CO2 and O-2 headspace concentrations. An increase in permeability, determined by conventional methods, suggested that both the non-polar and the polar polymers were plasticized by fermented milk. The plasticization was, however, modest and undetectable when the polyethylene tensile test data were analysed.

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