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  • 1. Adamus, Grazyna
    et al.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Höglund, Anders
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Kowalczuk, Marek
    Albertsson, Ann-Christine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    MALDI-TOF MS Reveals the Molecular Level Structures of Different Hydrophilic-Hydrophobic Polyether-esters2009In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 10, no 6, p. 1540-1546Article in journal (Refereed)
    Abstract [en]

    Multi- and triblock copolymers based on 1,5-dioxepan-2-one/epsilon-caprolactone (DXO/CL) were investigated by MALDI-TOF MS to determine the influence of copolymer composition and architecture on the molecular structures at the individual chain level. The copolymer compositions, average block lengths, and molecular weights were determined by H-1 and C-13 NMR and by SEC, respectively. The structures of polyether-ester oligomers (linear, cyclic) as well as the chemical structures of their end groups were established on the basis of their MALDI-TOF mass spectra. The mass spectrum of PDXO homopolymer was relatively simple, however, complex mass spectra were obtained in the case of multi- and triblock copolymers and the mass spectra clearly discerned the molecular level effect of copolymer composition and copolymer type.

  • 2.
    Adolfsson, Karin H.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hassanzadeh, Salman
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Valorization of cellulose and waste paper to graphene oxide quantum dots2015In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 5, no 34, p. 26550-26558Article in journal (Refereed)
    Abstract [en]

    Biobased graphene oxide quantum dots (GOQD) were derived from cellulose via carbon nanospheres (CN) as intermediate products. Solid CN were synthesized from cellulose through microwave-assisted hydrothermal degradation of alpha-cellulose with H2SO4 as a catalyst at 160 degrees C. The obtained CN were further utilized for the synthesis of GOQD by a two-step reaction including 30 minutes of sonication followed by heating at 90 degrees C under O-rich acidic conditions (HNO3). This process broke down the 3D CN to 2D GOQD. The size of the synthesized GOQD was controlled by the heating time, reaching a dot diameter of 3.3 nm and 1.2 nm after 30 and 60 minutes of heating, respectively. The synthesis process and products were characterized by multiple analytical techniques including FTIR, TGA, SEM, TEM, XPS, XRD, BET, DLS and AFM. Interesting optical properties in aqueous solutions were demonstrated by UV/Vis and fluorescence spectroscopy. Finally we demonstrated that corresponding GOQD can be synthesized from waste paper. This production route thus uses renewable and cheap starting materials and relatively mild synthesis procedures leads to instant nanometric production of 2D dots. In addition it enables recycling of low quality waste to value-added products.

  • 3.
    Adolfsson, Karin H.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Xie, L.
    Hassanzadeh, Salman
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Pettersson, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Zero-Dimensional and Highly Oxygenated Graphene Oxide for Multifunctional Poly(lactic acid) Bionanocomposites2016In: ACS Sustainable Chemistry & Engineering, ISSN 2168-0485, Vol. 4, no 10, p. 5618-5631Article in journal (Refereed)
    Abstract [en]

    The unique strengths of 2D graphene oxide nanosheets (GONSs) in polymer composites are thwarted by nanosheet agglomeration due to strong intersheet attractions. Here, we reveal that shrinking the planar size to 0D graphene oxide quantum dots (GOQDs), together with the intercalation of rich oxygen functional groups, reduces filler aggregation and enhances interfacial interactions with the host polymer. With poly(lactic acid) (PLA) as a model matrix, atomic force microscopy colloidal probe measurements illustrated that a triple increase in adhesion force to PLA was achieved for GOQDs (234.8 nN) compared to GONSs (80.4 nN), accounting for the excellent exfoliation and dispersion of GOQDs in PLA, in contrast to the notable agglomeration of GONSs. Although present at trace amount (0.05 wt %), GOQDs made a significant contribution to nucleation activity, mechanical strength and ductility, and gas barrier properties of PLA, which contrasted the inferior efficacy of GONSs, accompanied by clear distinction in film transparency (91% and 50%, respectively). Moreover, the GOQDs with higher hydrophilicity accelerated the degradation of PLA by enhancing water erosion, while the GONSs with large sheet surfaces gave a higher hydrolytic resistance. Our findings provide conceptual insights into the importance of the dimensionality and surface chemistry of GO nanostructures in the promising field of bionanocomposites integrating high strength and multifunction (e.g., enhanced transparency, degradation and gas barrier).

  • 4.
    Albertsson, Ann-Christine
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Erlandsson, Bengt
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Karlsson, Sigbritt
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Molecular weight changes and polymeric matrix changes correlated with the formation of degradation products in biodegraded polyethylene1999In: Journal of environmental polymer degradation, ISSN 1064-7546, E-ISSN 1572-8900, Vol. 64, p. 91-99Article in journal (Refereed)
    Abstract [en]

    The molecular weight changes in abiotically and biotically degraded LDPE and LDPE modified with starch and/or prooxidant were compared with the formation of degradation products, The samples were thermooxidized for 6 days at 100 degrees C to initiate degradation and then either inoculated with Arthobacter paraffineus or kept sterile. After 3.5 years homologous series of mono- and dicarboxylic acids and ketoacids were identified by GC-MS in abiotic samples, while complete disappearance of these acids was observed in biotic environments. The molecular weights of the biotically aged samples were slightly higher than the molecular weights of the corresponding abiotically aged samples, which is exemplified by the increase in (M) over bar(n) from 5200 g/mol for a sterile sample with the highest amount of prooxidant to 6000 g/mol for the corresponding biodegraded sample. The higher molecular weight in the biotic environment is explained by the assimilation of carboxylic acids and low molecular weight polyethylene chains by microorganisms. Assimilation of the low molecular weight products is further confirmed by the absence of carboxylic acids in the biotic samples. Fewer carbonyls and more double bonds were seen by FTIR in the biodegraded samples, which is in agreement with the biodegradation mechanism of polyethylene.

  • 5.
    Albertsson, Ann-Christine
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Groning, M.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Emission of volatiles from polymers - A new approach for understanding polymer degradation2006In: Journal of polymers and the environment, ISSN 1064-7546, E-ISSN 1572-8900, Vol. 14, no 1, p. 8-13Article in journal (Refereed)
    Abstract [en]

    Emission of low molar mass compounds from different polymeric materials was determined and the results from the volatile analysis were applied to predict the degree of degradation and long-term properties, to determine degradation rates and mechanisms, to differentiate between biotic and abiotic degradation and for quality control work. Solid-phase microextraction and solid-phase extraction together with GC-MS were applied to identify and quantify the low molar mass compounds. Volatiles were released and monitored at early stages of degradation before any matrix changes were observed by e.g. SEC, DSC and tensile testing. The analysis of volatiles can thus also be applied to detect small differences between polymeric materials and their susceptibility to degradation. The formation of certain degradation products correlated with the changes taking place in the polymer matrix, these indicator products could, thus, be analysed to rapidly predict the degree of degradation in the polymer matrix and further to predict the long-term properties and remaining lifetime of the product.

  • 6.
    Albertsson, Ann-Christine
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Gröning, Mikael
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Chromatographic analysis as a tool for predicting material performance2005In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, p. 247-248Article in journal (Other academic)
  • 7.
    Albertsson, Ann-Christine
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Degradable polymers and their interaction with the environment2007In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 223, p. 566-567Article in journal (Other academic)
  • 8.
    Albertsson, Ann-Christine
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Designed to degrade Suitably designed degradable polymers can play a role in reducing plastic waste2017In: Science, ISSN 0036-8075, E-ISSN 1095-9203, Vol. 358, no 6365, p. 872-873Article in journal (Refereed)
  • 9.
    Alin, Jonas
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Combined Chromatographic and Mass Spectrometric Toolbox for Fingerprinting Migration from PET Tray during Microwave Heating2013In: Journal of Agricultural and Food Chemistry, ISSN 0021-8561, E-ISSN 1520-5118, Vol. 61, no 6, p. 1405-1415Article in journal (Refereed)
    Abstract [en]

    A combined chromatographic and mass spectrometric toolbox was utilized to determine the interactions between poly(ethylene terephthalate) (PET) food packaging and different food simulants during microwave heating. Overall and specific migration was determined by combining weight loss measurements with gas chromatography-mass spectrometry (GC-MS) and electrospray ionization mass spectrometry (ESI-MS). This allowed mapping of low molecular weight migrants in the molecular range up to 2000 g/mol. Microwave heating caused significantly faster migration of cyclic oligomers into ethanol and isooctane as compared to migration during conventional heating at the same temperature. This effect was more significant at lower temperature at which diffusion rates are generally lower. It was also shown that transesterification took place between PET and ethanol during microwave heating, leading to formation of diethyl terephthalate. The detected migrants included cyclic oligomers from dimer to hexamer, in most cases containing extra ethylene glycol units, and oxidized Irgafos 168. ESI-MS combined with CID MS-MS was an excellent tool for structural interpretation of the nonvolatile compounds migrating to the food simulants. The overall migration was below the overall migration limit of 10 mg/dm(2) set by the European commission after 4 h of microwave heating at 100 degrees C in all studied food simulants.

  • 10.
    Alin, Jonas
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Microwave heating causes rapid degradation of antioxidants in polypropylene packaging leading to greatly increased specific migration to food simulants as shown by ESI-MS and GC-MS2011In: Journal of Agricultural and Food Chemistry, ISSN 0021-8561, E-ISSN 1520-5118, Vol. 59, no 10, p. 5418-5427Article in journal (Refereed)
    Abstract [en]

    Microwave heating of commercial microwavable polypropylene packaging in contact with fatty food simulants caused significant antioxidant degradation and increased specific migration as shown by electrospray ionization-mass spectrometry (ESI-MS) and gas chromatography-mass spectrometry (GC-MS). Degradation of the antioxidants Irgafos 168 and Irganox 1010 was not detected during conventional heating of polypropylene packaging at the same temperature. The migration into aqueous food simulants was primarily restricted by the water solubility of the migrants. Using isooctane as fatty food simulant caused significant swelling and greatly enhanced overall migration values compared to the other fatty food simulant, 99.9% ethanol, or the aqueous food simulants 10% ethanol, 3% acetic acid, or water. ESI-MS spectra clearly reflected the overall migration values, and the number and amount of compounds detected decreased as the hydrophilicity of the food simulant increased. ESI-MS was shown to be an excellent tool for the analysis of semivolatile migrants and a good complement to GC-MS analysis of volatile migrants.

  • 11.
    Alin, Jonas
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Migration from polycarbonate packaging to food simulants during microwave heating2012In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 97, no 8, p. 1387-1395Article in journal (Refereed)
    Abstract [en]

    The interactions between polycarbonate (PC) packaging and different food simulants during microwave heating were evaluated by identifying the compounds migrating into aqueous, alcoholic and fatty food simulants. The migration of compounds, such as 9,9-dimethylxanthene and m-tert-butyl-phenol, from the PC package to ethanol and isooctane increased significantly during microwave heating as compared to conventional heating. The increase in migration can be explained by degradation caused by microwave heating and/or stronger food simulant interactions. Depending on the food simulant the migrants were quantified either by multiple headspace–solid-phase micro-extraction (MHS-SPME) or direct injection in combination with gas chromatography-mass spectrometry. A partial least squares (PLS) regression model was developed to predict the extraction efficiency for headspace–solid-phase micro-extraction (HS-SPME) of food package migrants from the analyte properties. The most significant property for prediction of the enrichment factors was the octanol-water partition coefficient (log Kow). Polydimethylsiloxane (PDMS) and polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibers were compared for the extraction of the migrants. High correlation was found between the PDMS and PDMS/DVB enrichment factors (R2=0.98), but the extraction by PDMS/DVB fiber was much more efficient compared to the extraction by PDMS fiber. The detection limits after SPME extraction by PDMS/DVB fiber were 1, 0.1 and 3 ng/L for 4-ethoxy-ethyl-benzoate, 2,4-di-tert-butyl-phenol and benzophenone, respectively.

  • 12.
    Alin, Jonas
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    The significant effect of polypropylene material on the migration of antioxidants from food container to food simulants2010Conference paper (Other academic)
  • 13.
    Alin, Jonas
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Type of Polypropylene Material Significantly Influences the Migration of Antioxidants from Polymer Packaging to Food Simulants During Microwave Heating2010In: Journal of Applied Polymer Science, ISSN 0021-8995, E-ISSN 1097-4628, Vol. 118, no 2, p. 1084-1093Article in journal (Refereed)
    Abstract [en]

    Three different polypropylene materials, polypropylene homopolymer (PP), propylene-ethylene random copolymer (PP-R), and propylene-ethylene copolymer (PP-C) are commonly used in plastic containers designed for microwave heating of food. Migration of antioxidants, Irganox 1010 and Irgafos 168, from PP. PP-R, and PP-C during microwave heating in contact with different food simulants was investigated by utilizing microwave assisted extraction (MAE) and high performance liquid chromatography (HPLC). The polypropylene material significantly influenced the migration rate, which decreased in the order of increasing degree of crystallinity in the materials. PP homopolymer was the most migration resistant of the studied materials especially in contact with fatty food simulants. The use of isooctane as fatty food simulant resulted in rapid depletion of antioxidants, while migration to another fatty food simulant, 96% ethanol, was much more limited. Migration to aqueous and acidic food simulants was in most cases under the detection limits irrespective of microwaving time and temperature. The diffusion coefficients were similar to what have been found previously under similar conditions but without microwaves. The effect of swelling was shown by the large increase in the calculated diffusion coefficients when isooctane was used as food simulant instead of 96% ethanol. (C) 2010 Wiley Periodicals, Inc. I Appl Polym Sci 118: 1084-1093,2010

  • 14.
    Aminlashgari, Nina
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. ABB, Sweden.
    Becerra, Marley
    KTH, School of Electrical Engineering (EES), Electromagnetic Engineering. ABB, Sweden.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Characterization of degradation fragments released by arc-induced ablation of polymers in air2016In: Journal of Physics D: Applied Physics, ISSN 0022-3727, E-ISSN 1361-6463, Vol. 49, no 5, article id 055502Article in journal (Refereed)
    Abstract [en]

    Polymers exposed to high intensity arc plasmas release material in a process called arc-induced ablation. In order to investigate the degradation fragments released due to this process, two different polymeric materials, poly(oxymethylene) copolymer (POM-C) and poly(methyl methacrylate) (PMMA), were exposed to a transient, high-power arc plasma in air. A small fraction of the ablated material drifting away from the arcing volume was deposited on a fixed glass substrate during the total duration of a 2 kA ac current semicycle. In addition, another fraction of the released material was deposited on a second moving substrate to obtain a time-resolved streak 'image' of the arc-induced ablation process. For the first time, mass spectra of degradation fragments produced by arc-induced ablation were obtained from the material deposited on the substrates by using laser desorption ionization time-of-flight mass spectrometry (LDI-ToF-MS). It was found that oligomers with mean molecular weight ranging between 400 and 600 Da were released from the surface of the studied polymers. The obtained spectra suggest that the detected degradation fragments of POM could be released by random chain scission of the polymer backbone. In turn, random chain scission and splitting-off the side groups are suggested as the main chemical mechanism leading to the release of PMMA fragments under arc-induced ablation.

  • 15.
    Aminlashgari, Nina
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Emerging Mass Spectrometric Tools for Analysis of Polymers and Polymer Additives2012In: Advances in Polymer Science, ISSN 0065-3195, E-ISSN 1436-5030, Vol. 248, p. 1-38Article in journal (Refereed)
    Abstract [en]

    The field of mass spectrometry has experienced enormous developments in the last few years. New interesting mass spectrometric techniques have arrived and there have been further developments in the existing methods that have opened up new possibilities for the analysis of increasingly complex polymer structures and compositions. Some of the most interesting emerging techniques for polymer analysis are briefly reviewed in this paper. These include new developments in laser desorption ionization techniques, like solvent-free matrix-assisted laser desorption ionization (solvent-free MALDI) and surface-assisted laser desorption ionization (SALDI) mass spectrometry, and the developments in secondary ion mass spectrometry (SIMS), such as gentle-SIMS and cluster SIMS. Desorption electrospray ionization (DESI) mass spectrometry and direct analysis in real time (DART) mass spectrometry offer great possibilities for analysis of solid samples in their native form, while mobility separation prior to mass spectrometric analysis in ion mobility spectrometry (IMS) mass spectrometry further facilitates the analysis of complex polymer structures. The potential of these new developments is still largely unexplored, but they will surely further strengthen the position of mass spectrometry as an irreplaceable tool for polymer characterization.

  • 16.
    Aminlashgari, Nina
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    SALDI-MS for analysis of polyester degradation products2012In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 244Article in journal (Other academic)
  • 17.
    Aminlashgari, Nina
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Surface Assisted Laser Desorption Ionization-Mass Spectrometry (SALDI-MS) for Analysis of Polyester Degradation Products2012In: Journal of the American Society for Mass Spectrometry, ISSN 1044-0305, E-ISSN 1879-1123, Vol. 23, no 6, p. 1071-1076Article in journal (Refereed)
    Abstract [en]

    Novel surface assisted laser desorption ionization-mass spectrometry (SALDI-MS) method was developed for rapid analysis of low molecular mass polyesters and their degradation products by laser desorption ionization-mass spectrometry. Three polycaprolactone materials were analyzed by the developed method before and after hydrolytic degradation. The signal-to-noise values obtained by SALDI-MS were 20-100 times higher compared with the ones obtained by using traditional MALDI-MS matrices. A clean background at low mass range and higher resolution was obtained by SALDI-MS. Different nanoparticle, cationizing agent, and solvent combinations were evaluated. Halloysite nanoclay and magnesium hydroxide showed the best potential as SALDI surfaces. The SALDI-MS spectrum of the polyester hydrolysis products was verified by ESI-MS. The developed SALDI-MS method possesses several advantages over existing methods for similar analyses.

  • 18.
    Aminlashgari, Nina
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Höglund, Odd V
    Borg, Niklas
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Degradation profile and preliminary clinical testing of a resorbable device for ligation of blood vessels2013In: Acta Biomaterialia, ISSN 1742-7061, E-ISSN 1878-7568, Vol. 9, no 6, p. 6898-904Article in journal (Refereed)
    Abstract [en]

    A resorbable device for ligation of blood vessels was developed and tested in vitro to reveal the degradation profile of the device and to predict the clinical performance in terms of adequate mechanical support during a healing period of I week. In addition, preliminary clinical testing was performed that showed complete hemostasis and good tissue grip of renal arteries in five pigs. The device was made by injection molding of poly(glycolide-co-trimethylene carbonate) triblock copolymer, and it consisted of a case with a locking mechanism connected to a partly perforated flexible band. A hydrolytic degradation study was carried out for 7, 30 and 60 days in water and buffer medium, following the changes in mass, water absorption, pH and mechanical properties. A new rapid matrix-free laser desorption ionization-mass spectrometry (LDI-MS) method was developed for direct screening of degradation products released into the degradation medium. The combination of LDI-MS and electrospray ionization-mass spectrometry analyses enabled the comparison of the degradation product patterns in water and buffer medium. The identified degradation products were rich in trimethylene carbonate units, indicating preferential hydrolysis of amorphous regions where trimethylene units are located. The crystallinity of the material was doubled after 60 days of hydrolysis, additionally confirming the preferential hydrolysis of trimethylene carbonate units and the enrichment of glycolide units in the remaining solid matrix. The mechanical performance of the perforated band was followed for the first week of hydrolysis and the results suggest that sufficient strength is retained during the healing time of the blood vessels.

  • 19.
    Aminlashgari, Nina
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Pal, Jit
    Sanwaria, Sunita
    Nandan, Bhanu
    Srivastava, Rajiv K.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Degradation product profiles of melt spun in situ cross-linked poly(epsilon-caprolactone) fibers2015In: Materials Chemistry and Physics, ISSN 0254-0584, E-ISSN 1879-3312, Vol. 156, p. 82-88Article in journal (Refereed)
    Abstract [en]

    In situ cross-linking of poly(epsilon-caprolactone) (PCL) fiber with bis-(epsilon-caprolactone-4-yl) (BCY) was shown to be a feasible approach to compensate for reduction in molar mass of PCL during melt-spinning. The effect of in situ cross-linking on the degradation profile of melt spun PCL fibers with different amounts of BCY was evaluated using electrospray ionization-mass spectrometry. Degradation of the cross-linked fibers was carried out in aqueous medium at 37 degrees C and 60 degrees C for different periods of time. The degradation profiles were then compared with uncross-linked fiber and 3D porous cross-linked film of PCL Interesting differences in the degradation product profiles with linear, cyclic or BCY-related low molar mass compounds were observed, clearly demonstrating the effect of cross-linking and processing on the degradation process and formation of water-soluble products. In addition the degradation product profiles demonstrated that in situ cross-linking is a feasible technique for counteracting degradation reactions during melt-spinning.

  • 20.
    Aminlashgari, Nina
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Shariatgorji, Mohammadreza
    Department of Analytical Chemistry, Stockholm University, Stockholm, Sweden.
    Ilag, Leopold L.
    Department of Analytical Chemistry, Stockholm University, Stockholm, Sweden.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Nanocomposites as novel surfaces for laser desorption ionization mass spectrometry2011In: Analytical Methods, ISSN 1759-9660, E-ISSN 1759-9679, Vol. 3, no 1, p. 192-197Article in journal (Refereed)
    Abstract [en]

    The possibility to utilize nanocomposite films as easy-to-handle surfaces for surface assisted laser desorption ionization-mass spectrometry (SALDI-MS) of small molecules, such as pharmaceutical compounds, was evaluated. The signal-to-noise values of acebutolol, propranolol and carbamazepine obtained on the nanocomposite surfaces were higher than the values obtained on plain PLA surface showing that the nanoparticles participate in the ionization/desorption process even when they are immobilized in the polymer matrix. The advantages of nanocomposite films compared to the free nanoparticles used in earlier studies are the ease of handling and reduction of instrument contamination since the particles are immobilized into the polymer matrix. Eight inorganic nanoparticles, titanium dioxide, silicon dioxide, magnesium oxide, hydroxyapatite, montmorillonite nanoclay, halloysite nanoclay, silicon nitride and graphitized carbon black at different concentrations were solution casted to films with polylactide (PLA). There were large differences in signal intensities depending on the type of drug, type of nanoparticle and the concentration of nanoparticles. Polylactide with 10% titanium oxide or 10% silicon nitride functioned best as SALDI-MS surfaces. The limit of detection (LOD) for the study was ranging from 1.7 ppm up to 56.3 ppm and the signal to noise relative standard deviations for the surface containing 10% silicon nitride was approximately 20-30%. Scanning electron microscopy demonstrated in most cases a good distribution of the nanoparticles in the polymer matrix and contact angle measurements showed increasing hydrophobicity when the nanoparticle concentration was increased, which could influence the desorption and ionization. Overall, the results show that nanocomposite films have potential as surfaces for SALDI-MS analysis of small molecules.

  • 21.
    Avalos, Arturo Salazar
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Odelius, Karin
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Superiorly Plasticized PVC/PBSA Blends through Crotonic and Acrylic Acid Functionalization of PVC2017In: Polymers, ISSN 2073-4360, E-ISSN 2073-4360, Vol. 9, no 3, article id 84Article in journal (Refereed)
    Abstract [en]

    Superior plasticization efficiency was achieved by a grafting from functionalization of the PVC backbone. This was deduced to a synergistic effect of internal plasticization and improved intermolecular interactions between PVC and an oligomeric poly(butylene succinate-co-adipate) ( PBSA) plasticizer. A mild grafting process for functionalization of the PVC chain by crotonic acid ( CA) or acrylic acid ( AA) was used. The formation of PVC-g-CA and PVC-g-AA was confirmed by FTIR and H-1 NMR. Grafting with the seemingly similar monomers, CA and AA, resulted in different macromolecular structures. AA is easily homopolymerized and long hydrophilic poly( acrylic acid) grafts are formed resulting in branched materials. Crotonic acid does not easily homopolymerize; instead, single crotonic acid units are located along the PVC chain, leading to basically linear PVC chains with pendant crotonic acid groups. The elongation of PVC-g-CA and PVC-g-AA in comparison to pure PVC were greatly increased from 6% to 128% and 167%, respectively, by the grafting reactions. Blending 20% ( w/w) PBSA with PVC, PVC-AA or PVC-CA further increased the elongation at break to 150%, 240% and 320%, respectively, clearly showing a significant synergistic effect in the blends with functionalized PVC. This is a clearly promising milestone towards environmentally friendly flexible PVC materials.

  • 22.
    Azwar, Edwin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Liquefied Wood Flour and Rice Bran as Polylactide AdditivesArticle in journal (Other academic)
  • 23.
    Azwar, Edwin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Tuning the mechanical properties of tapioca starch by plasticizers, inorganic and agro-waste derived fillers2012In: Polymer science, ISSN 0965-545X, Vol. 2012, no Article ID 463298Article in journal (Refereed)
    Abstract [en]

    Mechanical properties of tapioca starch-based films were tuned by different additives and additive combinations. The additives included plasticizers (glycerol, sorbitol, and citric acid), inorganic fillers (halloysite and kaolin), and agrowaste-based fillers (milled wood flour and rice bran). In addition, new biobased additives were prepared from wood flour and rice bran through liquefaction reaction. Through different additive combinations, starch-based materials with significant differences in tensile properties were designed. Addition of halloysite nanoclay resulted in materials with improved tensile strength at break and rather low strain at break. The effect of kaolin on tensile strength was highly dependent on the used plasticizer. However, in most combinations the addition of kaolin resulted in materials with intermediate tensile strength and strain at break values. The addition of milled wood flour and rice bran improved the tensile strength, while the addition of liquefied fillers especially liquefied rice bran increased the strain at break indicating that liquefied rice bran could have potential as a plasticizer for starch blends.

  • 24.
    Azwar, Edwin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Vuorinen, Eino
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Pyrolysis-GC-MS reveals important differences in hydrolytic degradation process of wood flour and rice bran filled polylactide composites2012In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 97, no 3, p. 281-287Article in journal (Refereed)
    Abstract [en]

    Pyrolysis-GC-MS of polylactide (PLA) biocomposites before and after hydrolytic degradation revealed prominent differences in the hydrolytic degradation process of rice bran and wood flour filled biocomposites. The water uptake and mass loss for polylactide/wood flour composites were similar to that of plain PLA. Pyrolysis-GC-MS, however, showed that on prolonged ageing the hydrolysis of PLA led to increased wood flour concentration in the remaining biocomposite matrices. In contrast, the polylactide/rice bran composites exhibited larger water uptake and higher mass loss. Pyrolysis-GC-MS and FTIR analysis proved that the higher mass loss was caused by migration of rice bran from the composites. The type of natural filler could thus greatly influence the degradation process and/or the stability of the materials in aqueous or humid environments.

  • 25.
    Azwar, Edwin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Yin, Bo
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Liquefied biomass derived plasticizer for polylactide2013In: Journal of chemical technology and biotechnology (1986), ISSN 0268-2575, E-ISSN 1097-4660, Vol. 88, no 5, p. 897-903Article in journal (Refereed)
    Abstract [en]

    BACKGROUND: The valorization of renewable agro-industrial residues and their further utilization for production of polymers and polymer additives is a highly attractive alternative for replacement of oil-based materials. RESULTS: Liquefied wood flour and rice bran derived esters were synthesized and evaluated as novel green plasticizers for polylactide (PLA). The liquefied wood flour ester (PWF) showed good miscibility with PLA and good plasticization efficiency as shown by differential scanning calorimetry (DSC) and tensile testing. Tensile strain at break increased from a few percent for pure PLA to over 100 and 300% for the materials containing 10 and 30 wt-% of PWF. The addition of PWF accelerated the hydrolysis rate of PLA as shown by faster weight loss during aging in water and faster formation of water-soluble lactic acid oligomers, which was shown by electrospray ionization mass spectrometry (ESI-MS) analysis of the migrants. The liquefied rice bran based product (PRB) was not miscible with PLA and it did not improve the elongation at break of PLA. Rice bran is generally rich in arabinoxylans with only secondary less reactive alcohol groups. The larger number of un-reacted hydroxyl-groups in PRB was confirmed by Fourier transform infrared (FTIR) spectroscopy and could explain the immiscibility with PLA. CONCLUSIONS: The results demonstrate that the synthesized liquefied wood flour derived plasticizer could have great potential as a biobased polylactide plasticizer.

  • 26.
    Backström, Eva
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Odelius, Karin
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Trash to Treasure: Microwave-Assisted Conversion of Polyethylene to Functional Chemicals2017In: Industrial & Engineering Chemistry Research, ISSN 0888-5885, E-ISSN 1520-5045, Vol. 56, no 50, p. 14814-14821Article in journal (Refereed)
    Abstract [en]

    An effective microwave-assisted process for recycling low-density polyethylene (LDPE) waste into value-added chemicals was developed. To achieve fast and effective oxidative degradation aimed at production of dicarboxylic acids, nitric acid was utilized as an oxidizing agent. Different conditions were evaluated, where recycling time and concentration of oxidizing agent were varied and the end products were characterized by FTIR, NMR, and HPLC. After just 1 h of microwave irradiation at 180 degrees C in relatively dilute nitric acid solution (0.1 g/mL), LDPE powder was totally degraded. This transformation led to few well-defined water-soluble products, mainly succinic, glutaric, and adipic acids, as well as smaller amounts of longer dicarboxylic acids, acetic acid, and propionic acid. The length of the obtained dicarboxylic acids could to some extent be tuned by adjusting the reaction time, temperature, and amount of oxidizing agent. Finally, the developed process was verified by recycling LDPE freezer bags as model LDPE waste. The freezer bags were converted mainly into dicarboxylic acids with a yield of 71%, and the carbon efficiency of the process was 37%. The developed method can, thus, contribute to a circular economy and offers new possibilities to increase the value of plastic waste.

  • 27.
    Benyahia Erdal, Nejla
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Adolfsson, Karin H.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Pettersson, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Green Strategy to Reduced Nanographene Oxide through Microwave Assisted Transformation of Cellulose2018In: ACS Sustainable Chemistry and Engineering, ISSN 2168-0485, Vol. 6, no 1, p. 1245-1255Article in journal (Refereed)
    Abstract [en]

    A green strategy for fabrication of biobased reduced nanographene oxide (r-nGO) was developed. Cellulose derived nanographene oxide (nGO) type carbon nanodots were reduced by microwave assisted hydrothermal treatment with superheated water alone or in the presence of caffeic acid (CA), a green reducing agent. The carbon nanodots, r-nGO and r-nGO-CA, obtained through the two different reaction routes without or with the added reducing agent, were characterized by multiple analytical techniques including FTIR, XPS, Raman, XRD, TGA, TEM, AFM, UV-vis, and DLS to confirm and evaluate the efficiency of the reduction reactions. A significant decrease in oxygen content accompanied by increased number of sp2 hybridized functional groups was confirmed in both cases. The synergistic effect of superheated water and reducing agent resulted in the highest C/O ratio and thermal stability, which also supported a more efficient reduction. Interesting optical properties were detected by fluorescence spectroscopy where nGO, r-nGO, and r-nGO-CA all displayed excitation dependent fluorescence behavior. r-nGO-CA and its precursor nGO were evaluated toward osteoblastic cells MG-63 and exhibited nontoxic behavior up to 200 μg mL-1, which gives promise for utilization in biomedical applications.

  • 28.
    Bor, Yasemin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Alin, Jonas
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Electrospray Ionization-Mass Spectrometry Analysis Reveals Migration of Cyclic Lactide Oligomers from Polylactide Packaging in Contact with Ethanolic Food Simulant2012In: Packaging technology & science, ISSN 0894-3214, E-ISSN 1099-1522, Vol. 25, no 7, p. 427-433Article in journal (Refereed)
    Abstract [en]

    Electrospray ionization-mass spectrometry analysis revealed rapid migration of cyclic oligomers from polylactide (PLA) packaging when stored in contact with 96% ethanol. The mass losses in contact with water, 3% acetic acid, 10% ethanol and isooctane were 3 to 5 times smaller and no migration of cyclic oligomers was observed. The presence of cyclic oligomers in the original PLA films and their solubility in ethanol, thus, explains the rapid mass loss for PLA in contact with ethanolic food simulant. On prolonged ageing no further mass loss was observed in 96% ethanol, whereas mass loss in aqueous food simulants increased because of hydrolysis of PLA matrix or the cyclic oligomers to water-soluble linear products. The mass losses were generally somewhat smaller for the stereocomplex material compared with the poly-l-lactide materials. Similar trend was observed for solvent uptakes, which is easily explained by the higher degree of crystallinity and stronger secondary interactions in the stereocomplex material. The use of ethanol as a fatty food simulant for PLA materials could, thus, lead to overestimation of the overall migration values.

  • 29.
    Bor, Yasemin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Alin, Jonas
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Polylactide stereocomplexation leads to reduced migration during microwave heating in contact with food simulants2014In: Journal of Food Engineering, ISSN 0260-8774, E-ISSN 1873-5770, Vol. 134, p. 1-4Article in journal (Refereed)
    Abstract [en]

    The effect of stereocomplexation on the stability and migration resistance of polylactide during microwave and conventional heating in contact with different food simulants was evaluated. The heating effects were followed through mass loss measurements, molecular weight measurements and identification of the individual migrants by electrospray ionization-mass spectrometry (ESI-MS). Increased mass losses were observed as a function of time and temperature, but approximately 50% smaller mass losses were always measured for PLA stereocomplex as compared to the corresponding regular PLEA material. The stability of the stereocomplex material was, thus, significantly higher. Microwave heating increased the mass loss as compared to the conventional heating at the same time and temperature. This effect was especially significant when 10% ethanol was used as food simulant instead of water. The amount of water-soluble migrants was in most cases under the detection limits, but when heating temperature was increased to 95 C, ESI-MS revealed the formation of homologous series of linear lactic acid oligomers. Results indicate that PEA stereocomplex materials could have potential in single-use microwave applications.

  • 30.
    Burman, Lina
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Albertsson, Ann-Christine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Indicator products and chromatographic fingerprinting: New tools for degradation state and lifetime estimation2008In: CHROMATOGRAPHY FOR SUSTAINABLE POLYMERIC MATERIALS: RENEWABLE, DEGRADABLE AND RECYCLABLE, Berlin: Springer Verlag , 2008, Vol. 211, p. 1-22Chapter in book (Refereed)
    Abstract [en]

    The demands on polymeric products are growing both with respect to their function and purity. There is a need for new high-throughput characterisation tools for rapid quality control and evaluation of materials. Precise control over degradation rate and service-life are also prerequisites for successful use of degradable polymers in an increasing number of applications. The chromatographic fingerprinting and indicator product concepts, presented in the current paper, are novel and attractive alternatives for rapid evaluation of the product quality, degradability, durability and service-life. The sensitivity of these techniques allows for detection of small initial changes in the materials and signs of early degradation. The possible applications include evaluation of different pro-oxidants or antioxidants, optimisation of processing parameters, evaluation of long-term properties or storage stability and lifetime prediction. The same principal could also be applied to process control and monitoring, acceptance or rejection of raw materials, intermediate and final products. The usefulness of indicator products and chromatographic fingerprinting is shown for estimation of the degradation state of degradable polyethylene. in addition, chromatographic fingerprinting together with multivariate data analysis is utilised to classify degradable polyethylene materials based on their incorporated pro-oxidant systems.

  • 31. Duch, J.
    et al.
    Kubisiak, P.
    Adolfsson, Karin H.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Golda-Cepa, M.
    Kotarba, A.
    Work function modifications of graphite surface via oxygen plasma treatment2017In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 419, p. 439-446Article in journal (Refereed)
    Abstract [en]

    The surface modification of graphite by oxygen plasma was investigated experimentally (X-ray diffraction, nanoparticle tracking analysis, laser desorption ionization mass spectrometry, thermogravimetry, water contact angle) and by molecular modelling (Density Functional Theory). Generation of surface functional groups (mainly –OHsurf) leads to substantial changes in electrodonor properties and wettability gauged by work function and water contact angle, respectively. The invoked modifications were analyzed in terms of Helmholtz model taking into account the theoretically determined surface dipole moment of graphite—OHsurf system (μ = 2.71 D) and experimentally measured work function increase (from 0.75 to 1.02 eV) to determine the –OH surface coverage (from 0.70 to 1.03 × 1014 groups cm−2). Since the plasma treatment was confined to the surface, the high thermal stability of the graphite material was preserved as revealed by the thermogravimetric analysis. The obtained results provide a suitable quantitative background for tuning the key operating parameters of carbon electrodes: electronic properties, interaction with water and thermal stability.

  • 32.
    Dånmark, Staffan
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Finne-Wistrand, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Schander, K.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Arvidson, K.
    Mustafa, K.
    Albertsson, Ann-Christine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    In vitro and in vivo degradation profile of aliphatic polyesters subjected to electron beam sterilization2011In: ACTA BIOMATERIALIA, ISSN 1742-7061, Vol. 7, no 5, p. 2035-2046Article in journal (Refereed)
    Abstract [en]

    Degradation characteristics in response to electron beam sterilization of designed and biodegradable aliphatic polyester scaffolds are relevant for clinically successful synthetic graft tissue regeneration Scaffold degradation in vitro and in vivo were documented and correlated to the macroscopic structure and chemical design of the original polymer The materials tested were of inherently diverse hydrophobicity and crystallinity poly(L-lactide) (poly(LLA)) and random copolymers from L-lactide and epsilon-caprolactone or 1.5-dioxepan-2-one, fabricated into porous and non-porous scaffolds After sterilization, the samples underwent hydrolysis in vitro for up to a year In vivo, scaffolds were surgically implanted into rat calvarial defects and retrieved for analysis after 28 and 91 days In vitro, poly(L-lactide-co-1, 5-dioxepan-2-one) (poly(LLA-co-DXO)) samples degraded most rapidly during hydrolysis, due to the pronounced chain-shortening reaction caused by the sterilization. This was indicated by the rapid decrease in both mass and molecular weight of poly(LLA-co-DXO). Poly(L-lactide-co-epsilon-caprolactone) (poly(LLA-co-CL)) samples were also strongly affected by sterilization, but mass loss was more gradual; molecular weight decreased rapidly during hydrolysis Least affected by sterilization were the poly(LLA) samples, which subsequently showed low mass loss rate and molecular weight decrease during hydrolysis. Mechanical stability varied greatly. poly(LLA-co-CL) withstood mechanical testing for up to 182 days, while poly(LLA) and poly(LLA-co-DXO) samples quickly became too brittle Poly(LLA-co-DXO) samples unexpectedly degraded more rapidly in vitro than in vivo. After sterilization by electron beam irradiation, the three biodegradable polymers present widely diverse degradation profiles, both in vitro and in vivo. Each exhibits the potential to be tailored to meet diverse clinical tissue engineering requirements

  • 33.
    Erdal, Nejla B.
    et al.
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymer Technology.
    Construction of Bioactive and Reinforced Bioresorbable Nanocomposites by Reduced Nano-Graphene Oxide Carbon Dots2018In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 19, no 3, p. 1074-1081Article in journal (Refereed)
    Abstract [en]

    Bioactive and reinforced poly(ϵ-caprolactone) (PCL) films were constructed by incorporation of cellulose derived reduced nanographene oxide (r-nGO) carbon nanodots. Two different microwave-assisted reduction routes in superheated water were utilized to obtain r-nGO and r-nGO-CA. For the latter, a green reducing agent caffeic acid (CA), was incorporated in the reduction process. The materials were extruded and compression molded to obtain proper dispersion of the carbon nanodots in the polymer matrix. FTIR results revealed favorable interactions between r-nGO-CA and PCL that improved the dispersion of r-nGO-CA. r-nGO, and r-nGO-CA endorsed PCL with several advantageous functionalities including improved storage modulus and creep resistance. The considerable increase in storage modulus demonstrated that the carbon nanodots had a significant reinforcing effect on PCL. The PCL films with r-nGO-CA were also evaluated for their osteobioactivity and cytocompatibility. Bioactivity was demonstrated by formation of hydroxyapatite (HA) minerals on the surface of r-nGO-CA loaded nanocomposites. At the same time, the good cytocompatibility of PCL was retained as illustrated by the good cell viability to MG63 osteoblast-like cells giving promise for bone tissue engineering applications.

  • 34.
    Feng, Zhaoxuan
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Simeone, Antonio
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Odelius, Karin
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Biobased Nanographene Oxide Creates Stronger Chitosan Hydrogels with Improved Adsorption Capacity for Trace Pharmaceuticals2017In: ACS Sustainable Chemistry & Engineering, ISSN 2168-0485, Vol. 5, no 12, p. 11525-11535Article in journal (Refereed)
    Abstract [en]

    A promising green strategy for the fabrication of fully biobased chitosan adsorbents for wastewater purification is presented. Nanographene oxide (nGO)-type carbon dots were derived from chitosan (nGOCS) or from cellulose (nGOCL) through a two-step process including microwave-assisted hydrothermal carbonization and oxidation. Finally, nGO were evaluated as biobased property enhancers in chitosan hydrogel adsorbents. Macroporous chitosan hydrogels were synthesized by cross-linking with genipin, and the incorporation of nGO into these hydrogels was shown to facilitate the cross-linking reaction leading to more robust 3D cross-linked networks. This was evidenced by the increased storage modulus and by the swelling ratio that decreased from 5.7 for pristine chitosan hydrogel to 2.6 for hydrogel with 5 mg/mL nGOCS and 3.3 for hydrogel with 5 mg/mL nGOCL. As a further proof of the concept the hydrogels were shown to be effective adsorbent for the common anti-inflammatory drug diclofenac sodium (DCF). Here, the addition of nGO promoted the DCF adsorption process leading to 100% removal of DCF after only 5 h. The synergistic effect of electrostatic interactions, hydrogen bonding, and pi-pi stacking could explain the high adsorption of DCF on the hydrogels. The developed biobased CS/nGO hydrogels are thus promising adsorbents with great potential for purification of trace pharmaceuticals from wastewater.

  • 35.
    Finne Wistrand, Anna
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Polylactide:  2011In: Handbook of Engineering and Speciality Thermoplastics: Polyethers and Polyesters / [ed] S. Thomas and V. P.M., Hoboken, NJ, USA: John Wiley & Sons, 2011, p. 349-376Chapter in book (Other academic)
    Abstract [en]

    The production of durable functional products without using petroleumbased raw materials is a focus of much academic research today but it is also prioritized by many industries. Many questions still remain concerning the use, production and properties of bio-based and/or degradable polymers and whether or not they are more environmentally friendly than oil-based products. Polylactide is a bio-based compostable thermoplastic that is considered as one of the most promising materials for replacement of traditional volume plastics. The properties of polylactide can be tuned to resemble polystyrene, poly(ethylene terephthalate) or polyolefins by controlling the stereochemistry by copolymerization or blending. This chapter reviews the life-cycle of polylactide based materials as well as the properties and applications. The recent trends in the area are also discussed.

  • 36. Golda-Cepa, M.
    et al.
    Aminlashgari, Nina
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Engvall, Klas
    KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Chemical Technology.
    Kotarba, A.
    LDI-MS examination of oxygen plasma modified polymer for designing tailored implant biointerfaces2014In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 4, no 50, p. 26240-26243Article in journal (Refereed)
    Abstract [en]

    A versatile polymer coating for biomaterials was fabricated by the mild oxygen plasma treatment of Chemical Vapour Deposited (CVD) parylene C. The surface properties were tailored while the excellent protective properties of the bulk were preserved. The species, formed due to the plasma functionalisation, were fingerprinted by a novel Laser Desorption/Ionisation-Mass Spectrometry (LDI-MS) method. Improved osteosarcoma cells (line MG-63) attachment and viability on a modified surface were demonstrated.

  • 37. Golda-Cepa, M.
    et al.
    Brzychczy-Wloch, M.
    Engvall, Klas
    KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Chemical Technology.
    Aminlashgari, Nina
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Kotarba, A.
    Microbiological investigations of oxygen plasma treated parylene C surfaces for metal implant coating2015In: Materials science & engineering. C, biomimetic materials, sensors and systems, ISSN 0928-4931, E-ISSN 1873-0191, Vol. 52, p. 273-281Article in journal (Refereed)
    Abstract [en]

    Parylene C surface was modified by the use of oxygen plasma treatment and characterized by microscopic and surface-sensitive techniques (E-SEM, AFM, XPS, LDI-TOF-MS, contact angle). The influence of the treatment on surface properties was investigated by calculations of surface free energy (Owens-Wendt method). Moreover, early adhesion (Culture Plate Method, Optical Microscopy Test) and biofilm formation ability (Cristal Violet Assay) on the parylene C surface was investigated. The bacteria strains which are common causative agents of medical device-associated infections (Staphylococcus aureus, Staphylococcus epidermidis and Pseudomonas aeruginosa - reference strains and clinical isolates) were used. It was concluded that chemical (oxygen insertion) and physical (nanotopography generation) changes, have a significant impact on the biocompatibility in terms of increased hydrophilicity (θw of unmodified sample = 88° ± 2°, θw of 60 min modified sample = 17.6° ± 0.8°) and surface free energy (SFE of unmodified sample = 42.4 mJ/m2, and for 60 min modified sample = 70.1 mJ/m2). At the same time, no statistical effect on biofilm production and bacteria attachment to the modified surface of any of the tested strains was observed.

  • 38. Golda-Cepa, M
    et al.
    Chorylek, A
    Chytrosz, P
    Brzychezy-Wloch, M
    Jaworska, J
    Kasperczyk, J
    Hakkarainen, Minna
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymer Technology.
    Engvall, Klas
    KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology.
    Kotarba, A
    Multifunctional PLGA/parylene C coating for implant materials – an integral approach for biointerface optimization2016In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 8, p. 22093-22105Article in journal (Refereed)
    Abstract [en]

    Functionalizing implant surfaces is critical for improving their performance. An integrated approach was employedto develop a multifunctional implant coating based on oxygen plasma-modified parylene C and drug-loaded, biodegradablepoly(DL-lactide-co-glycolide) (PLGA). The key functional attributes of the coating (i.e., anti-corrosion, biocompatible, antiinfection,and therapeutic) were thoroughly characterized at each fabrication step by spectroscopic, microscopic, and biologicmethods and at different scales, ranging from molecular, through the nano- and microscales to the macroscopic scale. Thechemistry of each layer was demonstrated separately, and their mutual affinity was shown to be indispensable for thedevelopment of versatile coatings for implant applications.

  • 39. Groning, M.
    et al.
    Eriksson, Henrik
    KTH, School of Computer Science and Communication (CSC), Numerical Analysis and Computer Science, NADA.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Albertsson, Ann-Christine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Phenolic prepreg waste as functional filter with antioxidant effect in polypropylene and polyamide-62006In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 91, no 8, p. 1815-1823Article in journal (Refereed)
    Abstract [en]

    Milled phenol-formaldehyde glass-fibre scrap (prepreg) was mixed with polypropylene (PP) and polyamide-6 (PA6). The oxidation induction time (OIT) of PP/prepreg composite measured by both chemiluminescence (CL) and Differential Scanning Calorimetry (DSC) was significantly longer than the oxidation induction time of unstabilised base PP. In addition, mechanical testing showed that the prepreg filter stabilised both PP and PA6 towards oxidation during long-term accelerated ageing. Headspace-gas chromatography/mass spectrometry (HS-GC/MS) showed that PP/prepreg composites emit somewhat larger amounts of volatile compounds compared to the reference PP/glass fibre composites, while the amount of volatile components emitted from PA6/prepreg composites was similar to the reference PA6/glass fibre composites. The new prepreg composites could have potential in thermally demanding applications especially if a secondary phosphite stabiliser is added to further increase the oxidative stability through synergy effects.

  • 40. Groning, M.
    et al.
    Hakkarainen, Minna
    KTH, Superseded Departments, Polymer Technology.
    Headspace solid-phase microextraction with gas chromatography/mass spectrometry reveals a correlation between the degradation product pattern and changes in the mechanical properties during the thermooxidation of in-plant recycled polyamide 6,62002In: Journal of Applied Polymer Science, ISSN 0021-8995, E-ISSN 1097-4628, Vol. 86, no 13, p. 3396-3407Article in journal (Refereed)
    Abstract [en]

    The increased susceptibility of in-plant recycled polyamide 6,6 toward thermooxidation was shown by headspace solid-phase microextraction with gas chromatography/mass spectrometry (HS-SPME/GC-MS), tensile testing, differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). A correlation between the deterioration in mechanical properties and the formation of degradation products due to thermooxidation was found, and the most prominent decrease in mechanical properties coincided with the largest increase in the abundance of degradation products. The recycled materials had a shorter induction period toward oxidation, and their mechanical properties deteriorated faster than the mechanical properties of virgin material. The same trend was observed with HS-SPME/GC-MS because degradation products were found for recycled materials after oxidation times shorter than those for virgin material. Furthermore, larger amounts of degradation products were formed in the recycled materials. The high sensitivity of HS-SPME/GC-MS as an analytical tool was demonstrated because it was able to detect changes caused by oxidation considerably earlier than the other methods. Unlike DSC and FTIR, it could also show differences between samples recycled for different times. Four groups of degradation products-cyclic imides, pyridines, chain fragments, and cyclopentanones-were identified in thermooxidized polyamide 6,6. After 1200 h of thermooxidation, 1-pentyl-2,5-pyrrolidinedione was the most abundant degradation product. Approximately four times more 1-pentyl-2,5-pyrrolidinedione was formed in polyamide recycled three times than in virgin polyamide. Pyridines and chain fragments behaved toward oxidation and repeated processing like cyclic imides; that is, their amounts increased during oxidation, and larger amounts were formed in recycled materials than in virgin material. The cyclopentanone derivatives were present already in unaged material, and their amounts decreased during oxidation. Cyclopentanones were not formed because of the thermooxidation of polyamide 6,6.

  • 41.
    Groning, Mikael
    et al.
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, Superseded Departments, Polymer Technology.
    Multiple headspace solid-phase microextraction of 2-cyclopentyl-cyclopentanone in polyamide 6.6: possibilities and limitations in the headspace analysis of solid hydrogen-bonding matrices2004In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1052, no 02-jan, p. 61-68Article in journal (Refereed)
    Abstract [en]

    The interactions between a polar analyte, 2-cyclopentyl-cyclopentanone, and a solid polar matrix, polyamide 6.6, during multiple headspace solid-phase microextraction (MHS-SPME) were studied. Strong hydrogen bonding between the analyte and the matrix was observed and shown to cause slow migration and adsorption of the analyte. These matrix effects led to erroneous quantitation despite the use of multiple headspace extraction. Addition of water disrupted the hydrogen bonding between the analyte and the matrix and a valid quantitation was achieved. The addition of water also increased the sensitivity and allowed the identification of 2,5-bis(cyclopentyl)-1-cyclopentanone. The amount of 2-cyclopentyl-cyclopentanone in five different polyamide 6.6 samples was measured using the developed multiple headspace solid-phase microextraction method with water-displacer. The measured concentrations were in the range of 1.44-15.61 mug/g. These concentrations were up to 30% higher than the concentrations measured after microwave-assisted extraction (MAE), which indicates incomplete recovery by MAE. The use of water as a displacer eliminated the matrix effects and complete recovery of the analyte was achieved by MHS-SPME.

  • 42. Gröning, M.
    et al.
    Hakkarainen, Minna
    KTH, Superseded Departments, Polymer Technology.
    Headspace solid-phase microextraction - a tool for new insights into the long-term thermo-oxidation mechanism of polyamide 6.62001In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 932, no 02-jan, p. 1-11Article in journal (Refereed)
    Abstract [en]

    Low-molecular-mass products formed. during thermo-oxidation of polyamide 6.6 at 100 degreesC were extracted by headspace solid-phase microextraction and identified by GC-MS. A total of 18 degradation products of polyamide 6.6 were identified. In addition some low-molecular-mass products originating from the lubricants were detected. The identified degradation products were categorized into four groups where compounds within each group contain the same structural feature. In groups A, B and C several new thermo-oxidation products of polyamide 6.6 were identified including cyclic imides, pyridines and structural fragments from the original polyamide chain. 1-Pentyl-2,5-pyrrolidinedione (pentylsuccinimide) showed the largest increase in abundance during oxidation. The cyclopentanones in group D were already present in the un-aged material. Their amounts decreased during ageing and they are thus not formed during thermo-oxidation of polyamide 6.6 at 100 degreesC. The identified thermo-oxidation products can be formed as a result of extensive oxidation of the hexamethylenediamine unit in the polyamide backbone. The degradation products pattern shows that the long-term thermo-oxidative degradation, just like thermal degradation and photo-oxidation of polyamide 6.6, starts at the N-vicinal methylene groups.

  • 43.
    Gröning, Mikael
    et al.
    KTH, Superseded Departments, Polymer Technology.
    Hakkarainen, Minna
    KTH, Superseded Departments, Polymer Technology.
    Correlation between emitted and total amount of 2-cyclopentyl-cyclopentanone in polyamide 6.6 allows rapid assessment by HS and HS-SPME under non-equilibrium conditions2004In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1052, no 02-jan, p. 151-159Article in journal (Refereed)
    Abstract [en]

    A correlation was found between the emitted and total amount of 2-cyclopentyl-cyclopentanone in polyamide 6.6. The emitted amounts were measured by GC-MS after headspace (HS) or headspace solid-phase microextraction (HS-SPME) and the total content was determined after microwave-assisted extraction (MAE). The correlation was valid also under non-equilibrium conditions, which allows rapid assessment of 2-cyclopentyl-cyclopentanone content in polyamide 6.6 by headspace techniques. The incubation time needed for non-equilibrium headspace analysis could be reduced from 5 h to 45 min if the PA66 granules were milled to powder prior to extraction. However, to reach equilibrium between the analyte in the solid sample and the headspace still required 12 h of incubation at 80degreesC. The long incubation time is explained by slow diffusion rate due to the strong hydrogen bonding between analyte and matrix and the relatively high crystallinity of polyamide 6.6. The headspace extraction profile showed several equilibrium-like patterns that are easily mistaken for the real equilibrium.

  • 44.
    Gröning, Mikael
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Albertsson, Ann-Christine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Quantitative determination of volatiles in polymers and quality control of recycled materials by static headspace techniques2008In: CHROMATOGRAPHY FOR SUSTAINABLE POLYMERIC MATERIALS: RENEWABLE, DEGRADABLE AND RECYCLABLE, Berlin: Springer Verlag , 2008, Vol. 211, p. 51-84Chapter in book (Refereed)
    Abstract [en]

    A presentation is given of headspace (HS) extraction and headspace solid-phase microextraction (HS-SPME) techniques and their combination with multiple headspace (MHS) extraction to enable quantitative determination of volatiles in solid polymer matrixes. As an example, the development of HS, HS-SPME, and MHS-SPME methods for extraction of volatiles from thermo-oxidized and/or recycled polyamide 6.6 is reviewed with special focus on the problems encountered when extracting analytes from solid-sample matrixes including excessively long equilibrium times and adsorption of analytes to the sample matrix. Examples are also given of the application of HS-SPME in quality control of recycled materials, in durability assessment of polymeric materials and in degradation studies.

  • 45.
    Gröning, Mikael
    et al.
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, Superseded Departments, Polymer Technology.
    Albertsson, Ann-Christine
    KTH, Superseded Departments, Polymer Technology.
    Recycling of glass fibre reinforced phenolic prepreg waste. part 1. Recovery and reuse of glass fibres in PP and PA62004In: Polymers & polymer composites, ISSN 0967-3911, E-ISSN 1478-2391, Vol. 12, no 6, p. 491-500Article in journal (Refereed)
    Abstract [en]

    The present paper describes a feasible process to reuse glass fibres separated from phenolic prepreg waste as reinforcing filler in polypropylene (PP) and polyamide 6 (PA6). Prior to compounding, the recovered glass fibres were cut into 50 mm long fibre bundles and surface treated with gamma-aminopropyltriethoxysilane (APS) for increased composite interfacial strength. Electron Spectroscopy for Chemical Analysis (ESCA) and Atomic Force Microscopy (AFM) showed that the silane coupling agent was attached to the surface of the glass fibres but the silane layer was somewhat uneven, probably due to the presence of small amounts of organic contaminants. In addition it was found necessary to clean the glass fibres from organic contaminants by thermal treatment in order to attach silane coupling agent to the surfaces. The tensile strengths obtained for PP and PA6 composites with 30 wt% filler level of surface treated recovered glass fibres were 49 MPa and 101 MPa, respectively. This should be compared to 30 MPa and 75 MPa for composites containing untreated glass fibres and 19 MPa and 52 MPa for pure PP and PA6. Addition of 5 wt% PP-g-MA compatibiliser to the PP composite increased the tensile strength by another 14%, i.e. to 56 MPa. The good interfacial compatibility achieved by APS surface treatment and compatibilisation was verified by Scanning Electron Microscopy (SEM).

  • 46.
    Gröning, Mikael
    et al.
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Hakkarainen, Minna
    KTH, Superseded Departments, Polymer Technology.
    Albertsson, Ann-Christine
    KTH, Superseded Departments, Polymer Technology.
    Recycling of glass-fibre reinforced phenolic prepreg waste. Part 2. Milled prepreg as functional filler in PP and PA62004In: Polymers & polymer composites, ISSN 0967-3911, E-ISSN 1478-2391, Vol. 12, no 6, p. 501-509Article in journal (Refereed)
    Abstract [en]

    Phenolic resin impregnated glass-fibre prepreg waste was milled and used as reinforcing filler in polypropylene (PP) and polyamide 6 (PA6). Prepreg was particularly suitable to be used as filler in PA6. The fibres were homogeneously distributed during compounding and the addition of 20 wt% prepreg increased the tensile strength of PA6 by 63%, from 52 MPa to 85 MPa. Milled prepreg alone did not significantly increase the tensile strength of PP. However, if compounded together with maleic anhydride grafted polypropylene (PP-g-MA, Epolene G3003) compatibiliser, prepreg can be used as reinforcing filler in PP as well. Addition of 20 wt% prepreg together with 5 wt% Epolene G3003 increased the tensile strength of PP from 26 MPa to 43 MPa. In order to mill the prepreg for compounding with thermoplastics it has to be cured. A 2 kg batch of prepreg had to be cured for at least 2 hours at 200 degreesC to prevent the phenolic resin from falling off the glass-fibres. Milling should be performed using screens with holes larger than 3 mm in diameter to reduce the amount of prepreg fibres shorter than 2 mm, as they jam the hopper when feeding the recyclate to the extruder. The initial prepreg fibre length is of little importance to the composite mechanical properties, as the fibres are shortened to approximately the same length during compounding.

  • 47.
    Hakkarainen, Minna
    KTH, Superseded Departments, Polymer Technology.
    Aliphatic polyesters: Abiotic and biotic degradation and degradation products2002In: Advances in Polymer Science, ISSN 0065-3195, E-ISSN 1436-5030, Vol. 157, p. 113-138Article, review/survey (Refereed)
    Abstract [en]

    This paper reviews the degradation behavior of aliphatic polyesters of current interest, including polylactide, polycaprolactone, poly(3-hydroxybutyrate) and their copolymers. Special focus is given to degradation products formed in different abiotic and biotic environments. The influence of processing and processing additives on the properties and degradation behavior is also briefly discussed.

  • 48.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Developments in multiple headspace extraction2007In: Journal of Biochemical and Biophysical Methods, ISSN 0165-022X, E-ISSN 1872-857X, Vol. 70, no 2, p. 229-233Article, review/survey (Refereed)
    Abstract [en]

    This paper reviews new developments in multiple headspace extraction (MHE), especially its combination with two miniaturized extraction techniques, solid-phase microextraction (SPME) and single-drop microextraction (SDME). The combination of the techniques broadens the applicability of SPME and SDME to quantitative determination of analytes in complex liquid and solid matrixes. These new methods offer several advantages over traditional liquid-solid, liquid-liquid and headspace extraction techniques. The potential applications include extraction of volatiles and semivolatiles from environmental and physiological samples and from different polymer products such as medical and biomedical materials, food packaging and building materials. The theoretical principals of the techniques are also briefly reviewed.

  • 49.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Electrospray Ionization-Mass Spectrometry for Molecular Level Understanding of Polymer Degradation2012In: Advances in Polymer Science, ISSN 0065-3195, E-ISSN 1436-5030, Vol. 248, p. 175-204Article in journal (Refereed)
    Abstract [en]

    The stability and durability of polymeric materials under different external influences (e.g., sunlight, humidity, heat, chemicals, or microorganisms) is of outmost importance in applications such as coatings, building materials, and automotive parts, whereas a rapidly degradable material is preferable in temporary short-term applications. There are considerable economic and environmental benefits if we can design polymers for short or long lifetimes as well as prevent the release of harmful substances from the materials during their lifetime. The recent developments in mass spectrometric techniques facilitate possibilities for molecular level characterization of the changes taking place in the polymer matrix as well as for identification of the released degradation products. This review presents an overview of the application of electrospray ionization-mass spectrometry (ESI-MS) for the analysis of polymer degradation. The great potential of the technique for revealing detailed insights into the degradative reactions taking place is demonstrated with examples ranging from degradable polymers and biomaterials to degradation of coatings, paints, polymer electrolyte membranes, food packaging, and materials in the nuclear industry.

  • 50.
    Hakkarainen, Minna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Migration of monomeric and polymeric PVC plasticizers2008In: Advances in Polymer Science, ISSN 0065-3195, E-ISSN 1436-5030, Vol. 211, p. 159-185Article, review/survey (Refereed)
    Abstract [en]

    This paper summarizes current literature on the migration of monomeric and polymeric PVC plasticizers from medical materials, food packaging, and toys. Especially highlighted is macromolecular engineering as a tool to increase the plasticizing efficiency and migration resistance for polymeric plasticizers. The effect of branching, molecular weight, end-group functionality, and polydispersity on plasticizer performance was evaluated by quantification of low-molecular-weight hydrolysis products, measurements of mechanical properties, weight loss, surface segregation, as well as the preservation of material properties during aging. A more migration-resistant polymeric plasticizer that also better preserved its material properties during aging was obtained by combining a low degree of branching, hydrolysis-protecting end-groups, and higher molecular weight.

123 1 - 50 of 140
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