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  • 1. Andreasson, B.
    et al.
    Forsstrom, J.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Determination of fibre pore structure: influence of salt, pH and conventional wet strength resins2005In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 12, no 3, 253-265 p.Article in journal (Refereed)
    Abstract [en]

    It has been shown, in the present investigation, that the two methods used to investigate the pore size distribution of unbleached chemical pulps, i.e. inverse size exclusion chromatography (ISEC) and nuclear magnetic resonance (NMR), give different average pore radius for the pores inside the fibre wall. This is due to the way in which these experiments are performed and the sensitivity of the methods to different types of pores in the cell wall. It was also shown that the two methods gave different results when changing the pH and the ionic strength of the pulp suspension. The pore radius, as detected with ISEC, decreased with both increasing ionic strength and decreasing pH, indicating a loose structure of the exterior of the fibrillar network. However, the pore radius as detected with NMR, was virtually unaffected when increasing the ionic strength, indicating a very rigid structure of the interior of the fibre wall. Decreasing pH though, lead to a decrease in pore radius indicating that upon protonation of the carboxylic groups in the fibre wall, the electrostatic repulsion is diminished and the average pore radius decreases. The NMR technique was also used to study wet strength aid penetration into the fibre wall. It was shown that wet strength aids with a small molecular weight, penetrated the fibre wall, as detected by a decrease in pore radius. It was also shown that addition of different wet strength aids increased the tensile index of the sheet and decreased the fibre strength, measured as zero span-strength of the sheets.

  • 2. Andreasson, B.
    et al.
    Forsstrom, J.
    Wågberg, Lars
    KTH, Superseded Departments, Fibre and Polymer Technology.
    The porous structure of pulp fibres with different yields and its influence on paper strength2003In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 10, no 2, 111-123 p.Article in journal (Refereed)
    Abstract [en]

    The porous structure of the interior of papermaking fibres is a well-known important property of the fibres. Changes of this structure will influence tensile and burst strength of paper formed from the fibres and a change in pore size of the pores within the fibre wall is also important for the ability of molecules to diffuse in and out of the fibre wall. Relevant examples of this latter effect are the removal of lignin during cooking and the addition of performance chemicals during papermaking. In this paper, pore sizes and the pore size distribution of unbleached softwood fibres have been studied. A well-characterised fibre material consisting of laboratory cooked spruce and pine pulp of various lignin contents was used. Pore size and pore size distribution were measured by studies of the relaxation behaviour of H-2 in fibres saturated with (H2O)-H-2. Beside this the total and surface charge of the fibres were also measured together with strength properties of papers from unbeaten fibres. For both pulps, there is a maximum in pore radius at a yield around 46%. Calculations of fibre wall volume from water retention values and yield levels show that there is a discontinuity in pore radius as a function of the fibre wall volume around a yield of 51%. It is suggested that this discontinuity is caused by the breakdown of the hemicellulose/ lignin matrix within the fibre wall at this yield level. The strength of the papers formed from the fibres shows a correlation with the surface charge of the fibres. Based on the change in surface charge with yield and the change in total charge with yield, this correlation is suggested to be due to an opening up of the external part of the fibre wall. This stresses the importance of the chemical composition and physical structure of the outer layer of the fibre wall.

  • 3.
    Aulin, Christian
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Gallstedt, Mikael
    Lindström, Tom
    Oxygen and oil barrier properties of microfibrillated cellulose films and coatings2010In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 17, no 3, 559-574 p.Article in journal (Refereed)
    Abstract [en]

    The preparation of carboxymethylated microfibrillated cellulose (MFC) films by dispersion-casting from aqueous dispersions and by surface coating on base papers is described. The oxygen permeability of MFC films were studied at different relative humidity (RH). At low RH (0%), the MFC films showed very low oxygen permeability as compared with films prepared from plasticized starch, whey protein and arabinoxylan and values in the same range as that of conventional synthetic films, e.g., ethylene vinyl alcohol. At higher RH's, the oxygen permeability increased exponentially, presumably due to the plasticizing and swelling of the carboxymethylated nanofibers by water molecules. The effect of moisture on the barrier and mechanical properties of the films was further studied using water vapor sorption isotherms and by humidity scans in dynamic mechanical analysis. The influences of the degree of nanofibrillation/dispersion on the microstructure and optical properties of the films were evaluated by field-emission scanning electron microscopy (FE-SEM) and light transmittance measurements, respectively. FE-SEM micrographs showed that the MFC films consisted of randomly assembled nanofibers with a thickness of 5-10 nm, although some larger aggregates were also formed. The use of MFC as surface coating on various base papers considerably reduced the air permeability. Environmental scanning electron microscopy (E-SEM) micrographs indicated that the MFC layer reduced sheet porosity, i.e., the dense structure formed by the nanofibers resulted in superior oil barrier properties.

  • 4.
    Bergenstrahle-Wohlert, Malin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    d'Ortoli, Thibault Angles
    Sjoberg, Nils A.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Widmalm, Goran
    Wohlert, Jakob
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    On the anomalous temperature dependence of cellulose aqueous solubility2016In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 23, no 4, 2375-2387 p.Article in journal (Refereed)
  • 5.
    Bergenstråhle-Wohlert, Malin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Berglund, Lars A.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Biocomposites. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Brady, John W.
    Larsson, Per Tomas
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Westlund, Per-Olof
    Wohlert, Jakob
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Concentration enrichment of urea at cellulose surfaces: results from molecular dynamics simulations and NMR spectroscopy2012In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 19, no 1, 1-12 p.Article in journal (Refereed)
    Abstract [en]

    A combined solid-state NMR and Molecular Dynamics simulation study of cellulose in urea aqueous solution and in pure water was conducted. It was found that the local concentration of urea is significantly enhanced at the cellulose/solution interface. There, urea molecules interact directly with the cellulose through both hydrogen bonds and favorable dispersion interactions, which seem to be the driving force behind the aggregation. The CP/MAS (13)C spectra was affected by the presence of urea at high concentrations, most notably the signal at 83.4 ppm, which has previously been assigned to C4 atoms in cellulose chains located at surfaces parallel to the (110) crystallographic plane of the cellulose I beta crystal. Also dynamic properties of the cellulose surfaces, probed by spin-lattice relaxation time (13)CT (1) measurements of C4 atoms, are affected by the addition of urea. Molecular Dynamics simulations reproduce the trends of the T (1) measurements and lends new support to the assignment of signals from individual surfaces. That urea in solution is interacting directly with cellulose may have implications on our understanding of the mechanisms behind cellulose dissolution in alkali/urea aqueous solutions.

  • 6.
    Butchosa, Núria
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Biocomposites.
    Zhou, Qi
    KTH, School of Biotechnology (BIO), Glycoscience. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Water redispersible cellulose nanofibrils adsorbed with carboxymethyl cellulose2014In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 6, 4349-4358 p.Article in journal (Refereed)
    Abstract [en]

    Cellulose nanofibrils (CNFs) are difficult to redisperse in water after they have been completely dried due to the irreversible agglomeration of cellulose during drying. Here, we have developed a simple process to prepare water-redispersible dried CNFs by the adsorption of small amounts of carboxymethyl cellulose (CMC) and oven drying. The adsorption of CMC onto CNFs in water suspensions at 22 and 121 °C was studied, and the adsorbed amount of CMC was measured via conductimetric titration. The water-redispersibility of dried CNFs adsorbed with different amounts of CMC was characterized by sedimentation test. Above a critical threshold of CMC adsorption, i.e. 2.3 wt%, the oven dried CNF–CMC sample was fully redispersible in water. The morphology, rheological, and mechanical properties of water-redispersed CNF–CMC samples were investigated by field emission scanning electron microscopy, viscosity measurement, and tensile test, respectively. The water-redispersed CNFs preserved the original properties of never dried CNFs. This new method will facilitate the production, transportation and storage, and large-scale industrial applications of CNFs.

  • 7.
    Carlsson, Linn
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Ingverud, Tobias
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Blomberg, Hanna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Carlmark, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Larsson, Per Tomas
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. Innventia AB, Sweden.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Surface characteristics of cellulose nanoparticles grafted by surface-initiated ring-opening polymerization of epsilon-caprolactone2015In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 22, no 2, 1063-1074 p.Article in journal (Refereed)
    Abstract [en]

    In this study, surface-initiated ring-opening polymerization has been employed for the grafting of epsilon-caprolactone from cellulose nanoparticles, made by partial hydrolysis of cellulose cotton linters. A sacrificial initiator was employed during the grafting reactions, to form free polymer in parallel to the grafting reaction. The degree of polymerization of the polymer grafts, and of the free polymer, was varied by varying the reaction time. The aim of this study was to estimate the cellulose nanoparticle degree of surface substitution at different reaction times. This was accomplished by combining measurement results from spectroscopy and chromatography. The prepared cellulose nanoparticles were shown to have 3.1 (+/- 0.3) % of the total anhydroglucose unit content present at the cellulose nanoparticle surfaces. This effectively limits the amount of cellulose that can be targeted by the SI-ROP reactions. For a certain SI-ROP reaction time, it was assumed that the resulting degree of polymerization (DP) of the grafts and the DP of the free polymer were equal. Based on this assumption it was shown that the cellulose nanoparticle surface degree of substitution remained approximately constant (3-7 %) and seemingly independent of SI-ROP reaction time. We believe this work to be an important step towards a deeper understanding of the processes and properties controlling SI-ROP reactions occurring at cellulose surfaces.

  • 8.
    Cervin, Nicholas Tchang
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Aulin, Christian
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Larsson, Per Tomas
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Ultra porous nanocellulose aerogels as separation medium for mixtures of oil/water liquids2012In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 19, no 2, 401-410 p.Article in journal (Refereed)
    Abstract [en]

    A novel type of sponge-like material for the separation of mixed oil and water liquids has been prepared by the vapour deposition of hydrophobic silanes on ultra-porous nanocellulose aerogels. To achieve this, a highly porous (> 99%) nanocellulose aerogel with high structural flexibility and robustness is first formed by freeze-drying an aqueous dispersion of the nanocellulose. The density, pore size distribution and wetting properties of the aerogel can be tuned by selecting the concentration of the nanocellulose dispersion before freeze-drying. The hydrophobic light- weight aerogels are almost instantly filled with the oil phase when selectively absorbing oil from water, with a capacity to absorb up to 45 times their own weight in oil. The oil can also be drained from the aerogel and the aerogel can then be reused for a second absorption cycle.

  • 9. Charani, P. Rezayati
    et al.
    Dehghani-Firouzabadi, M.
    Afra, E.
    Blademo, A.
    Naderi, A.
    Lindström, Tom
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Production of microfibrillated cellulose from unbleached kraft pulp of Kenaf and Scotch Pine and its effect on the properties of hardwood kraft: microfibrillated cellulose paper2013In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 20, no 5, 2559-2567 p.Article in journal (Refereed)
    Abstract [en]

    This work investigated the effect of using Kenaf bast fibre kraft pulps compared to Scotch Pine kraft pulps for producing microfibrillated cellulose (MFC) and its employment for improving mechanical and physical properties of handsheets made from unbleached kraft hardwood pulp. It was shown that MFC based on Kenaf fibres can be produced at higher consistencies [> 5 % (w/w)] compared to when Scotch Pine is employed [a parts per thousand 2 % (w/w)] as raw material. The possibility of using a higher consistency when processing Kenaf is beneficial for the processing in microfluidizers. The rheological properties of the products were shown to be consistent with what is known for MFC-based systems. The studies indicate that the mechanical properties of handsheets from unbleached kraft hardwood pulp can be improved by replacing part of the unbleached kraft hardwood pulp fibres with either unbleached kraft Kenaf pulp or unbleached Scotch Pine kraft pulp. However, the same levels of improvements were obtained when using only a small amount [a parts per thousand 6 % (w/w)] of MFC based on Kenaf or Scotch Pine, when introduced into the system either as a dry strength additive or by coating pre-made handsheets. Finally, it was shown that the incorporation of MFC in handsheets decreases the air-permeability; this effect became amplified when the MFC was applied as a coating onto the handsheets.

  • 10. Chen, Pan
    et al.
    Ogawa, Yu
    Nishiyama, Yoshiharu
    Bergenstråhle-Wohlert, Malin
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Mazeau, Karim
    Alternative hydrogen bond models of cellulose II and IIII based on molecular force-fields and density functional theory2015In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 22, no 3, 1485-1493 p.Article in journal (Refereed)
    Abstract [en]

    Alternative hydrogen-bond structures were found for cellulose II and IIII based on molecular dynamics simulations using four force fields and energy optimization based on density functional theory. All the modeling results were in support to the new hydrogen-bonding network. The revised structures of cellulose II and IIII differ with the fiber diffraction models mainly in the orientation of two hydroxyl groups, namely, OH2 and OH6 forming hydrogen-bond chains perpendicular to the cellulose molecule. In the alternative structures, the sense of hydrogen bond is inversed but little difference can be seen in hydrogen bond geometries. The preference of these alternative hydrogen bond structures comes from the local stabilization of hydroxyl groups with respect to the beta carbon. On the other hand when simulated fiber diffraction patterns were compared with experimental ones, the current structure of cellulose II with higher energy and the alternative structure of cellulose IIII with lower energy were in better agreement.

  • 11. Colombani, A.
    et al.
    Djerbi, Soraya
    KTH, Superseded Departments, Biotechnology.
    Bessueille, L.
    Blomqvist, Kristina
    KTH, Superseded Departments, Biotechnology.
    Ohlsson, Anna
    KTH, Superseded Departments, Biotechnology.
    Berglund, Torkel
    KTH, Superseded Departments, Biotechnology.
    Teeri, Tuula
    KTH, Superseded Departments, Biotechnology.
    Bulone, V.
    In vitro synthesis of (1→3)-β-D-glucan (callose) and cellulose by detergent extracts of membranes from cell suspension cultures of hybrid aspen2004In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 11, no 3-4, 313-327 p.Article in journal (Refereed)
    Abstract [en]

    The aim of this work was to optimize the conditions for in vitro synthesis of (1 --> 3)-beta-D-glucan (callose) and cellulose, using detergent extracts of membranes from hybrid aspen (Populus tremula x tremuloides) cells grown as suspension cultures. Callose was the only product synthesized when CHAPS extracts were used as a source of enzyme. The optimal reaction mixture for callose synthesis contained 100 mM Mops buffer pH 7.0, 1 mM UDP-glucose, 8 mM Ca2+, and 20 mM cellobiose. The use of digitonin to extract the membrane-bound proteins was required for cellulose synthesis. Yields as high as 50% of the total in vitro products were obtained when cells were harvested in the stationary phase of the growth curve, callose being the other product. The optimal mixture for cellulose synthesis consisted of 100 mM Mops buffer pH 7.0, 1 mM UDP-glucose, 1 mM Ca2+, 8 mM Mg2+, and 20 mM cellobiose. The in vitro beta-glucans were identified by hydrolysis of radioactive products, using specific enzymes. C-13-Nuclear magnetic resonance spectroscopy and transmission electron microscopy were also used for callose characterization. The (1-->3)-beta-D-glucan systematically had a microfibrillar morphology, but the size and organization of the microfibrils were affected by the nature of the detergent used for enzyme extraction. The discussion of the results is included in a short review of the field that also compares the data obtained with those available in the literature. The results presented show that the hybrid aspen is a promising model for in vitro studies on callose and cellulose synthesis.

  • 12.
    Cunha, Ana Gisela
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Zhou, Qi
    KTH, School of Biotechnology (BIO), Glycoscience. KTH, School of Biotechnology (BIO), Centres, Albanova VinnExcellence Center for Protein Technology, ProNova. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Larsson, Per Tomas
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. INNVENTIA AB, Sweden.
    Berglund, Lars A.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Topochemical acetylation of cellulose nanopaper structures for biocomposites: mechanisms for reduced water vapour sorption2014In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 4, 2773-2787 p.Article in journal (Refereed)
    Abstract [en]

    Moisture sorption decreases dimensional stability and mechanical properties of polymer matrix biocomposites based on plant fibers. Cellulose nanofiber reinforcement may offer advantages in this respect. Here, wood-based nanofibrillated cellulose (NFC) and bacterial cellulose (BC) nanopaper structures, with different specific surface area (SSA), ranging from 0.03 to 173.3 m(2)/g, were topochemically acetylated and characterized by ATR-FTIR, XRD, solid-state CP/MAS C-13-NMR and moisture sorption studies. Polymer matrix nanocomposites based on NFC were also prepared as demonstrators. The surface degree of substitution (surface-DS) of the acetylated cellulose nanofibers is a key parameter, which increased with increasing SSA. Successful topochemical acetylation was confirmed and significantly reduced the moisture sorption in nanopaper structures, especially at RH = 53 %. BC nanopaper sorbed less moisture than the NFC counterpart, and mechanisms are discussed. Topochemical NFC nanopaper acetylation can be used to prepare moisture-stable nanocellulose biocomposites.

  • 13. Djahedi, Cyrus
    et al.
    Bergenstrahle-Wohlert, Malin
    Berglund, Lars A.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Wohlert, Jakob
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Role of hydrogen bonding in cellulose deformation: the leverage effect analyzed by molecular modeling2016In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 23, no 4, 2315-2323 p.Article in journal (Refereed)
  • 14.
    Djerbi, Soraya
    et al.
    KTH, Superseded Departments, Biotechnology.
    Aspeborg, Henrik
    KTH, Superseded Departments, Biotechnology.
    Nilsson, Peter
    KTH, Superseded Departments, Biotechnology.
    Blomqvist, Kristina
    KTH, Superseded Departments, Biotechnology.
    Teeri, Tuula
    KTH, Superseded Departments, Biotechnology.
    Identification and expression analysis of genes encoding putative cellulose synthases (CesA) in the hybrid aspen, Populus tremula (L.) × P. tremuloides (Michx.)2004In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 11, no 3-4, 301-312 p.Article in journal (Refereed)
    Abstract [en]

    Cellulose is synthesized in plant cell walls by large membrane-bound protein complexes proposed to contain several copies of the catalytic subunit of the cellulose synthase, CesA. Here we report identification of 10 distinct CesA genes within a database of 100,000 ESTs of the hybrid aspen, Populus tremula (L.) x P. tremuloides (Michx.). Expression analyses in normal wood undergoing xylogenesis and in tension wood indicate xylem specific expression of four putative CesA isoenzymes, PttCesA1, PttCesA3-1, PttCesA3-2 and PttCesA9. Both the protein sequences and the expression profiles of PttCesA3-1 and PttCesA3-2 are very similar, and they may thus represent redundant copies of an enzyme with essentially the same function. Further, one of the generally more constitutively expressed CesA genes, PttCesA2, seems to be activated on the opposite side of a tension wood induced stem, while PttCesA6 appears to be more specific for leaf tissues. The rest of the hybrid aspen CesA genes were found to be relatively evenly expressed over the poplar tissues hereby studied.

  • 15.
    Enebro, Jonas
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Momcilovic, Dane
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Siika-Aho, Matti
    VTT Technical Research Center of Finland, Espoo.
    Karlsson, Sigbritt
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Investigation of endoglucanase selectivity on carboxymethyl cellulose by mass spectrometric techniques2009In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 16, no 2, 271-280 p.Article in journal (Refereed)
    Abstract [en]

    The benefits of applying cellulose selective enzymes as analytical tools for chemical structure characterization of cellulose derivatives have been frequently addressed over the years. In a recent study the high selectivity of cellulase Cel45A from Trichoderma reesei (Tr Cel45A) was utilized for relating the chemical structure to the flow properties of carboxymethyl cellulose (CMC). However, in order to take full advantage of the enzymatic hydrolysis the enzyme selectivity on the cellulose substrate must be further investigated. Therefore, the selectivity of Tr Cel45A on CMC was studied by chemical sample preparation of the enzyme products followed by mass spectrometric chemical structure characterization. The results strongly suggest that, in accordance with recent studies, also this highly selective endoglucanase is able to catalyze hydrolysis of glucosidic bonds adjacent to mono-substituted anhydroglucose units (AGUs). Furthermore, the results also indicate that substituents on the nearby AGUs will affect the hydrolysis.

  • 16. Falt, S.
    et al.
    Wågberg, Lars
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Vesterlind, E. L.
    Larsson, Per Tomas
    Model films of cellulose II - improved preparation method and characterization of the cellulose film2004In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 11, no 2, 151-162 p.Article in journal (Refereed)
    Abstract [en]

    An optimization study of the preparation of spin-coated cellulose model films from the NMMO/DMSO system on silicon wafers has been made. The study shows that the cellulose concentration in the solution determines the cellulose film thickness and that the temperature of the solution affects the surface roughness. A lower solution temperature results in a lower surface roughness at cellulose concentrations below 0.8%. Using the described method, it is possible to prepare films with thicknesses of 30-90 nm with a constant surface roughness by changing the cellulose concentration, i.e. by dilution with DMSO. On these films, water has a contact angle less than 20degrees and about 50% of the material can, according to CP/MAS C-13-NMR spectroscopy on corresponding fibrous material, be considered to consist of crystalline cellulose II type material. It has further been shown that AFM can be used to determine the thickness of cellulose films, in both dry and wet states. In this method, the difference in height between the top surface and the underlying wafer has been measured at an incision made into the cellulose film. The cellulose films have also been spin-coated with the same technique as on the silicon oxide wafer onto the crystal in a quartz crystal microbalance (QCM). These model films were found to be suitable for swelling measurements with the QCM. The films were very stable during this type of measurement and films with different amounts of charges gave different swelling responses depending on their charges. As expected, films with a higher charge showed a higher swelling.

  • 17. Gellerstedt, F.
    et al.
    Wågberg, Lars
    Gatenholm, P.
    Swelling behaviour of succinylated fibers2000In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 7, no 1, 67-86 p.Article in journal (Refereed)
    Abstract [en]

    The swelling behaviour of cellulosic fibers bearing various amounts of carboxylic groups introduced by succinylation was studied as a function of pH. Upon an increase of pH, the perimeter of the succinylated fibers expanded as measured with the Wilhelmy plate technique. The fibers pass two pH regimes of increased expansion, pH = 5 and pH = 9. These pH levels correlate with the conductometric titration, which reveals two inflection points in both the pH and conductivity values for the succinylated fibers. Determinations of fiber saturation points (FSP) confirm that the cell wall is largely affected by increased pH. Analysis of the fibers with ESEM (Environmental Scanning Electron Microscope) showed that bundles of fibrils were released from the surface of the succinylated fibers at higher pH. Wilhelmy measurements also showed that the surface roughness was more than doubled in fibers succinylated for 12 h as pH rose from 3.2 to 10. These results indicate that, as the charge of the fibers is increased, the swelling forces reach such levels of magnitude that they overcome the structural network forces holding the fiber wall together. The methodology applied can hence be used to quantify the fundamental gel properties of the fiber wall.

  • 18.
    Gimåker, Magnus
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Adsorption of polyallylamine to lignocellulosic fibres: effect of adsorption conditions on localisation of adsorbed polyelectrolyte and mechanical properties of resulting paper sheets2009In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 16, no 1, 87-101 p.Article in journal (Refereed)
    Abstract [en]

    Cationic polyallylamine (PAH), was adsorbed onto lignocellulosic fibres, and a fluorescent label on the polyelectrolyte enabled its location to be shown by confocal fluorescence microscopy. The adsorption time and ionic strength were varied to study their effect on the localisation of the adsorbed PAH. The microscopy showed that a long adsorption time, 24 h, and a high ionic strength, 10(-1) M NaCl + 5 x 10(-3) M NaHCO3 or higher, resulted in the adsorption of polyallylamine throughout the fibre walls. Shorter adsorption times and/or lower ionic strength resulted in adsorption only to the fibre exterior. By preparing sheets from fibres with polyelectrolyte adsorbed either to the exterior parts or into the fibre cell wall and testing their mechanical behaviour, a link was established between the localisation of adsorbed polyelectrolyte and the mechanical properties. Adsorption to the fibre exterior led to an increase in tensile strength and strain at break. The creep deformation at 90%RH was also slightly reduced by the adsorption of low molecular weight PAH (15 kDa). When polyallylamine was adsorbed throughout the wall of the lignocellulosic fibres, the mechanical properties were not however improved and the creep deformation at 90%RH actually increased somewhat.

  • 19. Gunnars, S.
    et al.
    Wågberg, Lars
    KTH, Superseded Departments, Pulp and Paper Technology.
    Stuart, M. A. C.
    Model films of cellulose: I. Method development and initial results2002In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 9, no 04-mar, 239-249 p.Article in journal (Refereed)
    Abstract [en]

    This report presents a new method for the preparation of thin cellulose films. NMMO (N- methylmorpholine- N-oxide) was used to dissolve cellulose and addition of DMSO (dimethyl sulfoxide) was used to control viscosity of the cellulose solution. A thin layer of the cellulose solution is spin- coated onto a silicon oxide wafer and the cellulose is precipitated in deionised water. The cellulose film is anchored onto the silicon oxide wafer by a saturated polymer layer. Among many different polymers tested, PVAm (polyvinylamine) and G- PAM (glyoxalated- polyacrylamide) worked well. The preparation of cellulose model films described in this paper resulted in films with thicknesses in the range 20- 270 nm and the thickness can be controlled by altering the concentration of cellulose solution by addition of different amounts of DMSO. The films were cleaned in deionised water and were found to be free from solvents by ESCA analysis and contact angle measurements. The molecular weight distribution of the cellulose surface material shows that there is only minor breakdown of the cellulose chains, mainly by cleavage of the longest molecular mass fraction and without creation of low molecular mass oligomers of glucose.

  • 20. Gunnarsson, Maria
    et al.
    Theliander, Hans
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. Chalmers University of Technology, Sweden.
    Hasani, Merima
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. Chalmers University of Technology, Sweden.
    Chemisorption of air CO2 on cellulose: an overlooked feature of the cellulose/NaOH(aq) dissolution system2017In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 24, no 6, 2427-2436 p.Article in journal (Refereed)
    Abstract [en]

    A natural abundance of the air CO2 in NaOH(aq) at low temperature was investigated in terms of cellulose-CO2 interactions upon cellulose dissolution in this system. An organic superbase, namely 1,8-diazabicyclo[5.4.0]undec-7-ene, DBU, known for its ability to incorporate CO2 in carbohydrates, was employed in order to shed light on this previously overlooked feature of NaOH(aq) at low temperature. The chemisorption of CO2 onto cellulose was investigated using spectroscopic methods in combination with suitable regeneration procedures. ATR-IR and NMR characterisation of regenerated celluloses showed that chemisorption of CO2 onto cellulose during its dissolution in NaOH(aq) takes place both with and without employment of the CO2-capturing superbase. The chemisorption was also observed to be reversible upon addition of water: CO2 desorbed when water was used as regenerating agent but could be preserved when instead ethanol was used. This finding could be an important parameter to take into consideration when developing processes for dissolution of cellulose based on this system.

  • 21.
    Halonen, Helena
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Larsson, Per Tomas
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Iversen, Tommy
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Mercerized cellulose biocomposites: A study of influence of mercerization on cellulose supramolecular structure, water retention value and tensile properties2013In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 20, no 1, 57-65 p.Article in journal (Refereed)
    Abstract [en]

    In this study the effect of the mercerization degree on the water retention value (WRV) and tensile properties of compression molded sulphite dissolving pulp was evaluated. The pulp was treated with 9, 10, or 11 % aqueous NaOH solution for 1 h before compression molding. To study the time dependence of mercerization the pulp was treated with 12 wt% aqueous NaOH for 1, 6 or 48 h. The cellulose I and II contents of the biocomposites were determined by solid state cross polarization/magic angle spinning carbon 13 nuclear magnetic resonance (CP/MAS 13C NMR) spectroscopy. By spectral fitting of the C6 and C1 region the cellulose I and II content, respectively, could be determined. Mercerization decreased the total crystallinity (sum of cellulose I and cellulose II content) and it was not possible to convert all cellulose I to cellulose II in the NaOH range investigated. Neither increased the conversion significantly with 12 wt% NaOH at longer treatment times. The slowdown of the cellulose I conversion was suggested as being the result from the formation of cellulose II as a consequence of coalescence of anti-parallel surfaces of neighboring fibrils (Blackwell et al. in Tappi 61:71–72, 1978; Revol and Goring in J Appl Polym Sci 26:1275–1282, 1981; Okano and Sarko in J Appl Polym Sci 30:325–332, 1985). Compression molding of the partially mercerized dissolving pulps yielded biocomposites with tensile properties that could be correlated to the decrease in cellulose I content in the pulps. Mercerization introduces cellulose II and disordered cellulose and lowered the total crystallinity reflected as higher water sensitivity (higher WRV values) and poorer stiffness of the mercerized biocomposites.

  • 22. Hansen, Natanya M. L.
    et al.
    Blomfeldt, Thomas O. J.
    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.
    Plackett, David V.
    Properties of plasticized composite films prepared from nanofibrillated cellulose and birch wood xylan2012In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 19, no 6, 2015-2031 p.Article in journal (Refereed)
    Abstract [en]

    Xylans, an important sub-class of hemicelluloses, represent a largely untapped resource for new renewable materials derived from biomass. As with other carbohydrates, nanocellulose reinforcement of xylans is interesting as a route to new bio-materials. With this in mind, birch wood xylan was combined with nanofibrillated cellulose (NFC) and films were cast with and without glycerol, sorbitol or methoxypolyethylene glycol (MPEG) as plasticizers. Microscopy revealed some NFC agglomeration in the composite films as well as a layered nanocellulose structure. Equilibrium moisture content in plasticized films increased with glycerol content but was independent of xylan:NFC ratio in unplasticized films. Sorbitol- and MPEG-plasticized films showed equilibrium moisture contents of approximately 10 wt% independent of plasticizer content. Tensile testing revealed increases in tensile strength with increased NFC content in the xylan:NFC composition range from 50:50 to 80:20 and plasticizer addition generally provided less brittle films. The oxygen permeability of unplasticized xylan-NFC films fell into a range which was similar to that for previously measured pure NFC films and was statistically independent of the xylan:NFC ratio. Water vapor permeability values of 1.9-2.8.10(-11) g Pa-1 m(-1) s(-1) were found for unplasticized composite films, but these values were significantly reduced in the case of films plasticized with 10-40 wt% sorbitol.

  • 23.
    Hollertz, Rebecca
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Arwin, Hans
    Faure, Bertrand
    Zhang, Yujia
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Bergström, Lennart
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Dielectric properties of lignin and glucomannan as determined by spectroscopic ellipsometry and Lifshitz estimates of non-retarded Hamaker constants2013In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 20, no 4, 1639-1648 p.Article in journal (Refereed)
    Abstract [en]

    We present in this study a quantitative estimate of the dispersive interactions between lignin, hemicellulose and cellulose, which are the dominating components in wood and also extensively used to produce paper and packaging materials. The dielectric properties in the UV-visible region of spin-coated films of pure lignin and glucomannan were determined by spectroscopic ellipsometry. The non-retarded Hamaker constants were estimated from the determined spectral parameters using Lifshitz theory for lignin and glucomannan interacting with cellulose, titania and calcium carbonate in vacuum, water and hexane. The Hamaker constants for the different combinations of cellulose, lignin and glucomannan fall within a relatively narrow range of 35-58 and 8-17 zJ, for the values in vacuum (air) and water, respectively. The estimated Hamaker constants for the interactions of the wood components with TiO2 and CaCO3, common additives in paper, in water range from 3 to 19 zJ, thus being similar in magnitude as the interactions between the wood components themselves. In contrast, the Hamaker constant is essentially zero for glucomannan interacting with calcium carbonate in hexane. The Hamaker constants for lignin, hemicellulose and cellulose determined in this study can provide information regarding the surface interactions important for e.g. adhesion, friction, swelling and wetting in paper processing as well as for the resulting behavior of paper products.

  • 24.
    Ibn Yaich, Anas
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Edlund, Ulrica
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Albertsson, Ann-Christine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Barriers from wood hydrolysate/quaternized cellulose polyelectrolyte complexes2015In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 22, no 3, 1977-1991 p.Article in journal (Refereed)
    Abstract [en]

    Biobased polyelectrolyte complexes (PECs) were prepared by mixing negatively charged O-acetyl-4-O-methylglucuronoxylan-rich wood hydrolysate (WH) and positively charged quaternized cellulose (QC) in aqueous solution. The WH was obtained as an aqueous process liquor of the hydrothermal treatment of birch wood chips and partially upgraded by membrane filtration and dialysis. Three QC derivatives with different degrees of quaternization were synthesized, characterized in terms of molecular weight, charge density, crystallinity and solubility, and utilized for PEC production. The WH/QC PECs were designed to form free-standing films with high oxygen barrier performance and good mechanical integrity. The impact of the QC degree of quaternization on the oxygen permeability at both 50 and 80 % relative humidity, water vapor permeability and tensile properties was investigated. Films with a tensile strain-to-break as high as 7 % and an oxygen permeability as low as 1.3 (cm(3) mu m)/(m(2) - day kPa) at 80 % relative humidity were achieved.

  • 25.
    Illergård, Josefin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Römling, Ute
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Ek, Monica
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Biointeractive antibacterial fibres using polyelectrolyte multilayer modification2012In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 19, no 5, 1731-1741 p.Article in journal (Refereed)
    Abstract [en]

    Contact-active antibacterial surfaces are a novel tool in the antibacterial battle. The preparation of such surfaces usually involves harsh reaction conditions and organic solvents. A more sustainable alternative would involve physical adsorption of water-soluble polyelectrolytes using a renewable substrate. Here, highly charged cationic polyvinylamines (PVAm), with or without hydrophobic modifications, have been adsorbed onto the naturally anionic cellulosic wood-fibres. To increase the amount of PVAm, polyelectrolyte multilayers were prepared using polyacrylic acid as the anionic polyelectrolyte. The modified fibres were characterised for PVAm content, water retention and antibacterial properties. The use of multilayers increased the total polymer content without notably reducing the water swelling. The fibres were shown to have excellent bioactive properties and reduced waterborne Escherichia coli and Bacillus subtilis by more than 99.9 %, which is a generally accepted definition of an antibacterial material. A large reduction in bacterial growth was observed upon addition of nutrients, although minor growth was detected after 24 h. The results further show that one adsorbed polymer layer was sufficient to obtain a contact-active surface, which makes the PVAm multilayer system seemingly unique. No polymer leaching from any of the samples was detected, indicating that the fibres work via a contact-active antibacterial mechanism. The results show the feasibility of constructing a sustainable antibacterial material using a renewable substrate and water-based solutions in the material construction process.

  • 26.
    Illergård, Josefin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Ek, Monica
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Contact-active antibacterial multilayers on fibres: a step towards understanding the antibacterial mechanism by increasing the fibre charge2015In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 22, no 3, 2023-2034 p.Article in journal (Refereed)
    Abstract [en]

    Contact-active antibacterial materials with irreversibly attached antibacterial agents have been developed as an environmentally friendly alternative to traditional biocide treatments. Of particular interest are materials fabricated through the physical adsorption of charged polymers. This simple method allows for the use of water-based processes and materials originating from renewable sources, e.g., cellulosic fibres. Furthermore, by varying the process parameters, such as ionic strength, it is possible to tune the properties of the adsorbed polymer layer. However, the underlying antibacterial mechanism remains obscure, and this hinders the rational design of antibacterial multilayers. To gain further insight into the antibacterial mechanisms of physically adsorbed multilayers of polyvinylamine and polyacrylic acid, the surface charge of cellulose fibres was increased via radical oxidation. This oxidation increased the amount of polymer that was adsorbed and resulted in increased antibacterial efficacy against both Escherichia coli and Bacillus subtilis compared with polymer-modified unoxidised fibres. Electron microscopy analysis of the E. coli adhered to the fibres revealed that the multilayer treatment resulted in elongated bacteria with deformed cell walls. This work demonstrates the importance of electrostatic interaction to the antibacterial effect of polymer-modified fibres.

  • 27. Jansson, Mikael
    et al.
    Danielsson, Sverker
    Saadatmand, Soheil
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Edlund, Ulrica
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Albertsson, Ann-Christine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
    Upgrading of wood pre-hydrolysis liquor for renewable barrier design: a techno-economic consideration2014In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 3, 2045-2062 p.Article in journal (Refereed)
    Abstract [en]

    A techno-economic assessment of an upgrading procedure and outtake of a pre-hydrolysate in a presumed dissolving pulp mill was performed. Pre-hydrolysis of spruce wood chips in pilot scale produced input data for energy and mass balances and was performed with and without subsequent membrane filtration to produce hydrolysate fractions rich in galactoglucomannan and with some lignin. The hydrolysate is a viable raw material for the production of renewable thin oxygen barrier films as demonstrated herein in the formulation of free standing films with very low oxygen permeability at both moderate and high relative humidities. Approximately 50,000 ton dry solid upgraded pre-hydrolysate suitable for production of oxygen barriers could be produced according to the presumed dissolving pulp mill producing about 500,000 air dry ton dissolving pulp per year and applying a liquor to wood ratio of 4:1. Utilization of the pre-hydrolysis liquor hence adds value to and realizes the dissolving plant as a biorefinery. A sensitivity analysis indicates that the market price of the upgraded pre-hydrolysate has the largest positive effect on the return on investment for separation and upgrading of a pre-hydrolysate. Increased investment cost and increased annuity factor show negative effects.

  • 28. Jardeby, K
    et al.
    Lennholm, Helena
    KTH, Superseded Departments, Fibre and Polymer Technology.
    Germgard, U
    Characterisation of the undissolved residuals in CMC-solutions2004In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 11, no 2, 195-202 p.Article in journal (Refereed)
    Abstract [en]

    The undissolved fibre and gel residuals that had not completely reacted to form fully dissolved carboxy-methyl cellulose (CMC) in the production of CMC were studied to clarify the reactivity of wood components in the pulp. The undissolved residuals, the pulp and the CMC were therefore analysed on the fibre level, the cell-wall level and the chemical composition level. The results may be interpreted as indicating that the presence of undissolved residuals in the CMS was not due to any chemical difference. The undissolved residuals were shown to consist mainly of swollen cell wall parts and some whole wood cells, mainly thick-walled compression wood and summerwood cells. They react more slowly in the mercerisation and etherification, probably because of a greater diffusion resistance due to their larger dimensions or to a more dense structure. These cells are assumed to be less accessible for chemical penetration, but they may also contain supramolecular structures that slow down the CMC reaction.

  • 29. Josefsson, T.
    et al.
    Lennholm, H.
    Gellerstedt, Göran
    KTH, Superseded Departments, Pulp and Paper Technology.
    Changes in cellulose supramolecular structure and molecular weight distribution during steam explosion of aspen wood2001In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 8, no 4, 289-296 p.Article in journal (Refereed)
    Abstract [en]

    We have studied the cellulose supramolecular structure in pulps obtained by steam explosion of aspen wood. The pulps were bleached with hydrogen peroxide in an OQP-sequence and characterised by size exclusion chromatography and (1)3C cross polarisation magic angle spinning (CP/MAS) NMR-spectroscopy. With CP/MAS-NMR-spectroscopy and chemometrics we were able to separate the supramolecular structural changes taking place during steam explosion into two independent processes. One process was related to the extent of processing and showed degradation and dissolution of cellulose, hemicellulose and lignin accompanied by an increase in cellulose content. The second process was displayed by pulps having molecular weights below approximately 100 000 and was interpreted as showing the removal of dislocations and an increase in crystalline and/or paracrystalline cellulose in the cellulose fibrils.

  • 30.
    Kasai, Wakako
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Morooka, Toshiro
    Ek, Monica
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Mechanical properties of films made from dialcohol cellulose prepared by homogeneous periodate oxidation2014In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 1, 769-776 p.Article in journal (Refereed)
    Abstract [en]

    2,3-Dialdehyde celluloses were prepared by homogeneous periodate oxidation in an aqueous solution of methylol cellulose. Since methylol cellulose stays dissolved in water for a certain time before decomposing gradually into regenerated cellulose, the oxidation reaction progressed homogeneously throughout the period. The resulting dialdehyde cellulose achieved an oxidation level of over 90 % in as little as 12 h. Reducing the dialdehyde celluloses with NaBH4 resulted in water-soluble dialcohol celluloses, which have an open-ring structure at the C2-C3 position. The dialcohol celluloses were characterized using nuclear magnetic resonance spectrometry, Fourier transform infrared spectroscopy, and differential scanning calorimetry. The T-g of the products decreased with increasing oxidation levels. The products might be processable, and unique tensile properties were obtained by cutting the C2-C3 bonds in the glucopyranose rings. The dialcohol celluloses prepared using a cast method yielded clear and transparent films which showed unique mechanical properties by tensile tests depending on the values of oxidation level.

  • 31. Kisonen, Victor
    et al.
    Xu, Chunlin
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Bollström, Roger
    Hartman, Jonas
    Rautkoski, Hille
    Nurmi, Maristiina
    Hemming, Jarl
    Eklund, Patrik
    Willför, Stefan
    O-acetyl galactoglucomannan esters for barrier coatings2014In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 6, 4497-4509 p.Article in journal (Refereed)
    Abstract [en]

    A major enhancement of grease and water vapor barrier properties was accomplished with a 1-10 g/m(2) coating of O-acetyl galactoglucomannan (GGM) ester or with GGM coatings applied as water dispersions on cartonboard. GGMs were esterified with phthalic and benzoic anhydrides, respectively. The novel phthalic esters of GGM (GGM-Ph) were characterized with HPLC, NMR, and matrix-assisted laser desorption/ionization with mass spectrometry (MALDI-TOF-MS). The degree of substitution of GGM-Ph was obtained by H-1 NMR, C-13 NMR, and HPLC. The GGM esters and GGM were coated onto cartonboard, and they demonstrated good moisture and very good grease resistance even with thin 1-3 g/m(2) coatings. The time for penetration of 0.1 % rapeseed oil was 54 h with the 2.4 g/m(2) coating thickness. The lowest water vapor transmission value was 39 g/m(2)/24 h with 9.7 g/m(2) coating. The GGM esters had clearly higher water resistance and slightly higher grease barrier values than native GGM. High-molar-mass-based GGM (50 kg/mol) and GGM-Ph rendered better water vapor and grease barrier properties than low-molar-mass GGM (9 kg/mol) and GGM-Ph. The GGM-based coatings can be safely used on an industrial scale as water was used as a solvent. As obtained from non-food-based side-stream wood-based resources, GGM and GGM esters project a sustainable and modern conception for barrier purposes in food packaging.

  • 32.
    Kulachenko, Artem
    et al.
    KTH, School of Engineering Sciences (SCI), Solid Mechanics (Dept.).
    Denoyelle, Thibaud
    KTH, School of Engineering Sciences (SCI), Solid Mechanics (Dept.).
    Galland, Sylvain
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Lindström, Stefan B.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. Linköping University, Sweden.
    Elastic properties of cellulose nanopaper2012In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 19, no 3, 793-807 p.Article in journal (Refereed)
    Abstract [en]

    Nanopaper is a transparent film made of network-forming nanocellulose fibers. These fibers are several micrometers long with a diameter of 4-50 nm. The reported elastic modulus of nanopaper often falls short of even conservative theoretical predictions based on the modulus of crystalline cellulose, although such predictions usually perform well for other fiber composite materials. We investigate this inconsistency and suggest explanations by identifying the critical factors affecting the stiffness of nanopaper. A similar inconsistency is found when predicting the stiffness of conventional paper, and it is usually explained by the effects introduced during drying. We found that the effect of the drying cannot solely explain the relatively low elastic modulus of nanopaper. Among the factors that showed the most influence are the presence of non-crystalline regions along the length of the nanofibers, initial strains and the three-dimensional structure of individual bonds.

  • 33.
    Larsson, Per A.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Berglund, Lars A.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Biocomposites. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Highly ductile fibres and sheets by core-shell structuring of the cellulose nanofibrils2014In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 1, 323-333 p.Article in journal (Refereed)
    Abstract [en]

    A greater ductility of cellulosic materials is important if they are to be used in increasingly advanced applications. This study explores the potential for using chemical core-shell structuring on the nanofibril level to alter the mechanical properties of cellulose fibres and sheets made thereof. The structuring was achieved by a selective oxidation of the cellulose C2-C3 bonds with sodium periodate, followed by a reduction of the aldehydes formed with sodium borohydride, i.e. locally transforming cellulose to dialcohol cellulose. The resulting fibres were morphologically characterised and the sheets made of these modified fibres were mechanically tested. These analyses showed a minor decrease in the degree of polymerisation, a significantly reduced cellulose crystal width and a greater ductility. At 27 % conversion of the available C2-C3 bonds, sheets could be strained 11 %, having a stress at break of about 90 MPa, and consequently a remarkable tensile energy absorption at rupture of about 9 kJ/kg, i.e. 3-4 times higher than a strong conventional paper. Zero-span tensile measurements indicated that the treatment increased the ductility not only of sheets but also of individual fibres. This suggests that the amorphous and molecularly more mobile dialcohol cellulose is located as a shell surrounding the crystalline core of the cellulose fibrils, and that, at deformations beyond the yield point, this facilitates plastic deformation both within and between individual fibres.

  • 34.
    Larsson, Per A.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Gimaker, Magnus
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    The influence of periodate oxidation on the moisture sorptivity and dimensional stability of paper2008In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 15, no 6, 837-847 p.Article in journal (Refereed)
    Abstract [en]

    The hygroexpansion of paper was significantly reduced, up to 28% lower amplitude of change when the paper was subjected to a change in relative humidity from 20 to 85% RH, by oxidation of the fibre wall. Never-dried bleached kraft fibres were oxidised with sodium periodate, which specifically oxidises the C2-C3 bond of 1,4-glucans so that the cellulose is partly converted into dialdehyde cellulose. Since both the dry and wet strength of laboratory sheets were significantly improved, the dry tensile strength increased from 24 kNm/kg up to 66 kNm/kg and the relative wet tensile strength increased from 1.5% up to 40%, it is suggested that the aldehydes form hemiacetal linkages within the fibre wall during the consolidation and drying of the sheets. The mechanical, hygroexpansive and moisture sorptive properties of the sheets made from the oxidised fibres were studied. The results showed that the main reason for the reduced hygroexpansion was a decrease in moisture sorptivity, i.e. when the sheets made of fibres with different degrees of cross-linking were subjected to the same change in relative humidity, the more cross-linked fibres showed a smaller change in moisture content. It was also shown that the hygroexpansion coefficient, i.e. the moisture-normalised dimensional change, was not significantly changed by the periodate oxidation, i.e. indicating that there are no improvement in dimensional stability if the paper is subjected to a specific amount of water.

  • 35.
    Larsson, Per A.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Diffusion-induced dimensional changes in papers and fibrillar films: influence of hydrophobicity and fibre-wall cross-linking2010In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 17, no 5, 891-901 p.Article in journal (Refereed)
    Abstract [en]

    The initial dimensional stability of paper measured as hydroexpansion, i.e. when paper is exposed to liquid water, has been considerably improved by combining a periodate-oxidation-induced cross-linking of the fibre wall with the subsequent adsorption of a hydrophobic polyelectrolyte multilayer consisting of three layers of poly(allylamine hydrochloride) and two layers of poly(acrylic acid). This reduced the rate of diffusion of water into the fibre wall at the same time as the diffusion distance was increased, i.e. the water has to diffuse all the way from the top of the sheet and not only from the individual fibre surfaces since capillary absorption was prevented. However, as a consequence, the hydrophobic sheets present a greater expansion maximum before contraction. It is suggested that this may be due to a higher moisture content in the top fibre layers of the hydrophobically modified papers than in the hydrophilic sheets, since all the water is concentrated to the top fibre layers of the hydrophobic papers. Sheets made from bleached kraft pulp or thermo-mechanical pulp as well as model sheets made from microfibrillated cellulose (MFC) were studied. The MFC-sheets were intended as a model of the fibre wall, i.e. a sheet without any fibre joints. The behaviour of the MFC-sheets was similar to that of ordinary sheets when subjected to water, which indicates that the properties of the fibre joints do not affect the hydroexpansion to any great content and that the expansion of the paper is directly linked to the expansion of the fibre wall.

  • 36.
    Larsson, Per A.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Influence of fibre-fibre joint properties on the dimensional stability of paper2008In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 15, no 4, 515-525 p.Article in journal (Refereed)
    Abstract [en]

    Measurements have been performed to clarify the connection between fibre-fibre joint properties and dimensional stability using laboratory sheets prepared from never-dried fibres, from heavily hornified fibres having a low molecular contact area between the fibres, and from both hornified and never-dried fibres treated with a polyelectrolyte multilayer (PEM) technique to increase the molecular contact area in the fibre-fibre joint. The influence of the drying mode, i.e. whether the sheets are dried freely or under restraint, was also evaluated. The results showed that neither paper strength nor fibre-fibre joint contact area had any significant influence on the dimensional stability of sheets dried under restraint. On the other hand, when the sheets were dried freely, the PEM-treated sheets expanded to the same extent as, or to an even greater extent than the non-PEM-treated sheets, even though they adsorbed less water for a given change in relative humidity. There was also a correlation between drying shrinkage and dimensional stability, where greater shrinkage was associated with a greater hygroexpansion in the freely dried sheets.

  • 37.
    Larsson, Per Tomas
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Svensson, Anna
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    A new, robust method for measuring average fibre wall pore sizes in cellulose I rich plant fibre walls2013In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 20, no 2, 623-631 p.Article in journal (Refereed)
    Abstract [en]

    A new, robust method for measuring the average pore size of water-swollen, cellulose I rich fibres is presented. This method is based on the results of solid-state NMR, which measures the specific surface area (area/solids mass) of water-swollen samples, and of the fibre saturation point (FSP) method, which measures the pore volume (water mass/solids mass) of water-swollen samples. These results are suitable to combine since they are both recorded on water-swollen fibres in excess water, and neither requires the assumption of any particular pore geometry. The new method was used for three model samples and reasonable average pore size measurements were obtained for all of them. The structural characterization of water-swollen samples was compared with the dry structure of fibres as revealed using BET nitrogen gas adsorption after a liquid exchange procedure and careful drying. It was concluded that the structure of the water-swollen fibres sets an upper limit on what is obtainable in the dry state.

  • 38.
    Le Normand, Myriam
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Moriana, Rosana
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Ek, Monica
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    The bark biorefinery: a side-stream of the forest industry converted into nanocomposites with high oxygen-barrier properties2014In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 6, 4583-4594 p.Article in journal (Refereed)
    Abstract [en]

    The purpose of the bark biorefinery concept is to upgrade the different constituents present in bark to multiple value-added bio-based products. Non-cellulosic polysaccharides (NCP) and cellulose nanocrystals (CNC) sequentially isolated from the inner bark of Norway spruce were used as raw materials for the formulation of renewable nanocomposites. The film formation abilities of NCP/CNC formulations prepared with different proportions of CNC were studied. Homogeneous transparent films with a glossy appearance were obtained when more than 30 wt% CNC was incorporated. The influence of the CNC content on the NCP/CNC films was assessed in terms of structural, thermal, mechanical and oxygen-barrier properties. All the films showed better performances with increasing CNC content, which was explained by the strong interactions between the two components. The effect on the film performances of adding sorbitol as a plasticizer was also evaluated. The presence of sorbitol decreased the thermal stability, the stiffness and the oxygen permeability of the films at 80 % RH. However, the addition of sorbitol enhanced the elongation of the films and further improved their oxygen-barrier properties at 50 % RH. The composite properties could thus be tailored by adding different amounts of sorbitol and CNC, resulting in all-carbohydrate materials with performances similar to or even better than the conventional barrier materials used in packaging.

  • 39.
    Lindh, Erik L.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.
    Salmén, Lennart
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Surface accessibility of cellulose fibrils studied by hydrogen-deuterium exchange with water2016In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 24, no 1, 21-33 p.Article in journal (Refereed)
    Abstract [en]

    A problem with cellulose-based materials is that they are highly influenced by moisture, leading to reduced strength properties with increasing moisture content. By achieving a more detailed understanding of the water–cellulose interactions, the usage of cellulose-based materials could be better optimized. Two different exchange processes of cellulose hydroxyl/deuteroxyl groups have been monitored by transmission FT-IR spectroscopy. By using line-shape-assisted deconvolution of the changing intensities, we have been able to follow the exchange kinetics in a very detailed and controlled manner. The findings reveal a hydrogen exchange that mainly is located at two different kinds of fibril surfaces, where the differences arise from the water accessibility of that specific surface. The slowly accessible regions are proposed to be located between the fibrils inside of the aggregates, and the readily accessible regions are suggested to be at the surfaces of the fibril aggregates. It was also possible to identify the ratio of slowly and readily accessible surfaces, which indicated that the average aggregate of cotton cellulose is built up by approximately three fibrils with an assumed average size of 12 × 12 cellulose chains. Additionally, the experimental setup enabled visualizing and discussing the implications of some of the deviating spectral features that are pronounced when recording FT-IR spectra of deuterium-exchanging cellulose: the insufficient red shift of the stretching vibrations and the vastly decreasing line widths.

  • 40.
    Lindström, Stefan
    et al.
    Linköping University, Sweden.
    Karabulut, Erdem
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Kulachenko, Artem
    KTH, School of Engineering Sciences (SCI), Solid Mechanics (Dept.), Solid Mechanics (Div.).
    Sehaqui, Houssine
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Mechanosorptive creep in nanocellulose materials2012In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 19, no 3, 809-819 p.Article in journal (Refereed)
    Abstract [en]

    The creep behavior of nanocellulose films and aerogels are studied in a dynamic moisture environment, which is crucial to their performance in packaging applications. For these materials, the creep rate under cyclic humidity conditions exceeds any constant humidity creep rate within the cycling range, a phenomenon known as mechanosorptive creep. By varying the sample thickness and relative humidity ramp rate, it is shown that mechanosorptive creep is not significantly affected by the through-thickness moisture gradient. It is also shown that cellulose nanofibril aerogels with high porosity display the same accelerated creep as films. Microstructures larger than the fibril diameter thus appear to be of secondary importance to mechanosorptive creep in nanocellulose materials, suggesting that the governing mechanism is found between molecular scales and the length-scales of the fibril diameter.

  • 41. Liu, Jun
    et al.
    Korpinen, Risto
    Mikkonen, Kirsi S.
    Willfor, Stefan
    Xu, Chunlin
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. Process Chemistry Centre, c/o Laboratory Wood and Paper Chemistry, Åbo Akademi University, Finland.
    Nanofibrillated cellulose originated from birch sawdust after sequential extractions: a promising polymeric material from waste to films2014In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 4, 2587-2598 p.Article in journal (Refereed)
    Abstract [en]

    The residual cellulose of wood processing waste, sawdust, which was leftover after sequential hot-water extraction processes to isolate hemicelluloses and lignin in a novel forest biorefinery concept, was explored as the starting material for preparation of a highly value-added polymeric material, nanofibrillated cellulose (NFC) also widely termed as cellulose nanofiber, which has provided an alternative efficient way to upgrade sawdust waste. The residual cellulose in sawdust was converted to a transparent NFC suspension in water through the 2,2,6,6-tetramethylpiperidine-1-oxyl radical/NaClO/NaBr oxidization approach. The resultant NFC with a dimension of ca. 5 nm in width and hundreds of nanometers in length were further processed into NFC films. The morphological features of the NFC suspension and its films were assessed by transmission electron microscopy and scanning electron microscopy. Highly even dispersion of NFC fibrils in the films originated from sawdust feasibly contributes to the outstanding mechanical performance of the films. NFC suspension with higher carboxylate content and its resultant NFC films were found to show higher transmission of light.

  • 42.
    Liu, Yingxin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. Stockholm Univ, Sweden.
    Gordeyeva, Korneliya
    Bergstrom, Lennart
    Steady-shear and viscoelastic properties of cellulose nanofibril-nanoclay dispersions2017In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 24, no 4, 1815-1824 p.Article in journal (Refereed)
    Abstract [en]

    We have investigated the steady-shear and viscoelastic properties of composite dispersions of cellulose nanofibrils (CNFs) with medium or high charge density and two different nanoclays, viz. rodlike sepiolite or plate-like bentonite. Aqueous dispersions of CNFs with medium charge density displayed significantly lower steady-state viscosity and storage modulus but higher gelation threshold compared with CNFs with high charge density. Dynamic light scattering (DLS) results showed that the apparent hydrodynamic radius of bentonite particles increased when CNFs were added, implying that CNFs adsorbed onto the amphoteric edges of the plate-like bentonite particles. The sepiolite network in CNF-sepiolite dispersions was relatively unaffected by addition of small amounts of CNFs, and DLS showed that the hydrodynamic radius of sepiolite did not change when CNFs were added. Addition of CNFs at concentrations above the gelation threshold resulted in drastic decrease of the steady-shear viscosity of the sepiolite dispersion, suggesting that the sepiolite network disintegrates and the rod-like clay particles are aligned also at low shear rate. The relative change in the rheological properties of the clay-based dispersions was always greater on addition of CNFs with high compared with medium charge density. This study provides insight into how the rheology of CNF-nanoclay dispersions depends on both the nanoclay morphology and the interactions between the nanoclay and nanocellulose particles, being of relevance to processing of nanocellulose-clay composites.

  • 43.
    López Durán, Vernica
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Larsson, Per A.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    On the relationship between fibre composition and material properties following periodate oxidation and borohydride reduction of lignocellulosic fibres2016In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 23, no 6, 3495-3510 p.Article in journal (Refereed)
    Abstract [en]

    Periodate oxidation followed by borohydride reduction was performed on four structurally different pulp fibres to clarify the effect of chemical composition on the structural and mechanical properties of sheets made from these fibres. The main purpose was to explore the possibility of extending the use of lignocellulose fibres in novel applications. The degree of oxidation, morphological changes, chemical and physical structure of the fibres, the supramolecular ordering of the cellulose and the mechanical performance of handsheets made from the fibres were studied. The results showed that both periodate oxidation and borohydride reduction are more reactive towards the carbohydrates of the fibres and as a result, there is an improvement in the tensile properties of the sheets. If the carbohydrates of the fibres are only periodate oxidised to produce dialdehydes, inter- and intra-fibre crosslinks can be formed, leading to paper with increase strength and higher stiffness. The borohydride reduction results in fibres and papers with a greater strength and ductility. It was also found that the characteristic ductility of these modified papers, emanating from the dialcohol cellulose produced, is limited with lignin-rich fibres.

  • 44.
    Magnusson, Mikael S.
    et al.
    KTH, School of Engineering Sciences (SCI), Solid Mechanics (Dept.). KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Östlund, Sören
    KTH, School of Engineering Sciences (SCI), Solid Mechanics (Dept.). KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Numerical evaluation of interfibre joint strength measurements in terms of three-dimensional resultant forces and moments2013In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 20, no 4, 1691-1710 p.Article in journal (Refereed)
    Abstract [en]

    The interfibre joint is one of the key elements in creating the strength of self-binding fibrous materials such as paper and board. In order evaluate the strength properties of interfibre joints using direct measurements, a greater understanding on how the mode of loading influences the results is desirable. The methods reported in the literature do not in general distinguish between the contributions of normal and shear stresses in the bonded region. This paper presents a numerical analysis procedure, based on the finite element method, for evaluating interfibre joint strength measurements in terms of the normal, shear, and moment loading components during testing. The target is to estimate the resultant forces and moments, that acts in the interfibre joint region at rupture, of Kraft pulp interfibre joints tested under two principally different modes of loading. The results show that for a typical interfibre joint test, modes of loading other than pure shear cannot, in general, be neglected, and are strongly dependent on the structural geometry of the fibre-fibre crosses. In addition, the resultant forces and moments were scaled in terms of the interface area and the twisting and bending resistance of the interface approximated as an ellipse to account for differences in interface area between the measurements. These scaled resultants were used to quantify how the mode of loading influences the relation between the amount of normal stress and the amount of shear stress that develop in the interfibre joint.

  • 45.
    Marais, Andrew
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Magnusson, Mikael S.
    KTH, School of Engineering Sciences (SCI), Solid Mechanics (Dept.). KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Joffre, Thomas
    Wernersson, Erik L. G.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    New insights into the mechanisms behind the strengthening of lignocellulosic fibrous networks with polyamines2014In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 21, no 6, 3941-3950 p.Article in journal (Refereed)
    Abstract [en]

    Polyelectrolytes have been used extensively in the papermaking industry for various purposes. Although recent studies have shown that polyamines can be efficient dry-strength additives, the mechanism governing the strength enhancement of paper materials following the adsorption of polyamines onto pulp fibres is still not well understood. In this study, the effect of the adsorption of polyallylamine hydrochloride (PAH) onto the surface of unbleached kraft pulp fibres was investigated on both the fibre and the network scale. Isolated fibre crosses were mechanically tested to evaluate the impact of the chemical additive on the interfibre joint strength on the microscopic scale and the effect was compared with that previously observed on the paper sheet scale. X-ray microtomography was used to understand structural changes in the fibrous network following the adsorption of a polyamine such as PAH. Using image analysis methods, it was possible to determine the number of interfibre contacts (or joints) per unit length of fibre as well as the average interfibre joint contact area. The results showed that the median interfibre joint strength increased by 18 % upon adsorption of PAH. This can be achieved both by a larger molecular contact area in the contact zones and by a stronger molecular adhesion. The addition of the polymer also increased the number of efficient interfibre contacts per sheet volume. This combination of effects is the reason why polyamines such as PAH can increase the dry tensile strength of paper materials.

  • 46.
    Marais, Andrew
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
    Wågberg, Lars
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    The use of polymeric amines to enhance the mechanical properties of lignocellulosic fibrous networks2012In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 19, no 4, 1437-1447 p.Article in journal (Refereed)
    Abstract [en]

    Cationic polyelectrolytes (polyallylamine and polyvinylamine with different molecular masses) were adsorbed onto lignocellulosic fibres from unbleached and unbeaten spruce chemical fibres with different kappa numbers to investigate the effects on the mechanical properties of the final paper materials. Adsorption isotherms were first established to determine the maximum quantity of polymer that could be adsorbed onto each type of fibre. Paper sheets were then made with different amounts of added polyelectrolyte, and the structural and mechanical properties of the sheets were investigated, as well as the effect of an extra heating. The use of fibres with different kappa numbers led to different responses in terms of adsorption, and thus to differences in the mechanical properties of the resulting sheets. The tensile strength index was significantly increased (almost 50 % improvement in the best case) as a consequence of this polyelectrolyte adsorption onto the fibres, even at as low an adsorption level as 2 mg/g. The heating of paper sheets for 10 min at 160 A degrees C was also shown to improve the tensile strength index by about 10 % for pulps with high kappa number.

  • 47. Martinez-Sanz, Marta
    et al.
    Olsson, Richard T.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Lopez-Rubio, Amparo
    Lagaron, Jose M.
    Development of electrospun EVOH fibres reinforced with bacterial cellulose nanowhiskers. Part I: Characterization and method optimization2011In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 18, no 2, 335-347 p.Article in journal (Refereed)
    Abstract [en]

    In the present study, hybrid electrospun EVOH fibres reinforced with bacterial cellulose nanowhiskers (BCNW) were developed and characterized. The nanowhiskers, obtained by sulphuric acid digestion of native bacterial cellulose mats generated by Gluconacetobacter xylinum, were morphologically characterized by SEM and optical microscopy with polarized light and revealed a highly crystalline structure of nanofibrils aggregates. XRD analyses suggested a crystalline structure corresponding to the cellulose I allomorph. It was also confirmed by means of FT-IR spectroscopy that amorphous regions were preferentially digested by the acid treatment, whereas TGA analyses showed a decrease in the thermal stability of the nanowhiskers most likely due to incorporation of sulphate groups and the inherent acidity remaining in the filler even after extensive washing cycles. A method was developed for improving the incorporation of BCNW within the EVOH electrospun fibres, consisting on the addition of the BCNW in the form of a centrifuged precipitate, versus the most conventionally employed freeze-dried nanowhiskers. DSC analyses showed a significant increase in the glass transition temperature of the composites during the second heating run, which may be related to the acidic character of the nanofiller. Finally, sonication was seen to enhance interfacial interaction but to reduce the incorporation of the filler in the matrix in the case of the centrifuged material.

  • 48. Mikkonen, K. S.
    et al.
    Mathew, A. P.
    Pirkkalainen, K.
    Serimaa, R.
    Xu, Chunlin
    KTH, School of Biotechnology (BIO), Glycoscience. Åbo Akademi University.
    Willför, S.
    Oksman, K.
    Tenkanen, M.
    Glucomannan composite films with cellulose nanowhiskers2010In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 17, no 1, 69-81 p.Article in journal (Refereed)
    Abstract [en]

    Spruce galactoglucomannans (GGM) and konjac glucomannan (KGM) were mixed with cellulose nanowhiskers (CNW) to form composite films. Remarkable effects of CNW on the appearance of the films were detected when viewed with regular and polarizing optical microscopes and with a scanning electron microscope. Addition of CNW to KGM-based films induced the formation of fiberlike structures with lengths of several millimeters. In GGM-based films, rodlike structures with lengths of several tens of micrometers were formed. The degree of crystallinity of mannan in the plasticized KGM-based films increased slightly when CNW were added, from 25 to 30%. The tensile strength of the KGM-based films not containing glycerol increased with increasing CNW content from 57 to 74 MPa, but that of glycerol-plasticized KGM and GGM films was not affected. Interestingly, the notable differences in the film structure did not appear to be related to the thermal properties of the films.

  • 49. Moberg, Tobias
    et al.
    Sahlin, Karin
    Yao, Kun
    KTH, School of Biotechnology (BIO), Glycoscience. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Geng, Shiyu
    Westman, Gunnar
    Zhou, Qi
    KTH, School of Biotechnology (BIO), Glycoscience. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
    Oksman, Kristiina
    Rigdahl, Mikael
    Rheological properties of nanocellulose suspensions: effects of fibril/particle dimensions and surface characteristics2017In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 24, no 6, 2499-2510 p.Article in journal (Refereed)
    Abstract [en]

    The rheological properties of aqueous suspensions based on three different nanocelluloses were compared. One system was obtained via acid hydrolysis (thus yielding crystalline nanocellulose, CNC) and the other two from mechanical shearing, but from different origins and subjected to different pretreatments. Of the latter two, one was considered to be a rather typical cellulose nanofibril (CNF) suspension whereas the other was a kind of intermediate between CNF and CNC. All three nanocellulose elements differed in dimensions as evident from transmission electron microscopy and atomic force microscopy. With regard to the length of the fibrils/particles, the three nanocelluloses formed three distinct groups with lengths between 200 and slightly more than 800 nm. The three cellulosic elements were also subjected to a TEMPO-mediated oxidation yielding a similar carboxylate content in the three systems. Furthermore, the TEMPO-oxidized elements were grafted with poly(ethylene glycol) (PEG). The amount of grafted PEG was about 35 wt%. The shear viscosity, the storage modulus and the loss modulus of suspensions of the unmodified, the TEMPO-oxidized and the grafted nanocelluloses were determined at room temperature and the solids content of the suspensions was varied between 0.7 and 2.0 wt%. It was concluded that the rheological properties varied significantly between the suspensions depending on the dimensions of the cellulosic elements and their surface characteristics. In this context, the length (or the aspect ratio) of the particles played a very important role.

  • 50.
    Moriana, Rosana
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Vilaplana, Francisco
    Ek, Monica
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
    Forest residues as renewable resources for bio-based polymeric materials and bioenergy: chemical composition, structure and thermal properties2015In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 22, no 5, 3409-3423 p.Article in journal (Refereed)
    Abstract [en]

    The potential of three different logging residues (woody chips, branches and pine needles) as renewable resources to produce environmentally friendly polymeric materials and/or biofuel has been critically evaluated in terms of their structure, chemical composition and thermal properties. Woody chips constitute the most attractive forest residue to be processed into polymeric materials in terms of their highest cellulose content, crystallinity and thermal stability. In contrast, pine needles and branches offer higher heating values and optimum product distribution for solid fuel applications due to their higher lignin content. In general, forest residual biomass has great potential for conversion into new added value products, such as composites or solid biofuel, thus constituting a sustainable waste management procedure from a biorefinery perspective. The correlation between the chemical and structural properties with the thermal/pyrolytic behavior of residual biomass offers valuable insights to assess their sustainable exploitation.

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