In this thesis, Atomic Force Microscopy (AFM) is used to characterize Micro Fibrillated Cellulose (MFC) produced by two different methods according to their size and shape. For one of these MFC-types, their interaction with the humidity in the atmosphere is investigated and their swelling is calculated. MFC is a relatively new material based on cellulose fibres extracted from wood. This study is performed in co-operation with Stora Enso research centre. Stora Enso is a renewable material company which uses mostly wood based raw materials in their production. The measured swelling is ~ 5 % and depends on the number of elementary fibrils included in the fibre. / Atomkraftsmikroskopi (AFM) har använts för att karakterisera Mikro Fibrillerad Cellulosa (MFC), som är producerad med två olika produktionsmetoder, med avseende på deras storlek och form. För en av dessa MFC-typer så är deras påverkan av en varierande fuktig atmosfär undersökt och deras svällning är uträknad. MFC är ett relativt nytt material baserat på cellulosafibrer från trä. Detta examensarbete är utfört i samarbete med Stora Enso forskningscentrum. Stora Enso är ett företag fokuserat på förnyelsebara material som använder mestadels träbaserade råmaterial i deras prodiktion. Den uppmätta svällningen är ~ 5 % och beror av antalet elementära fibriller som ingår i fibern.

The growing market of mobile electronic devices, renewable off-grid energy sources and electric vehicles requires high-performance energy storage devices. Rechargeable batteries are usually the first choice due to their high energy density. However, supercapacitors have a higher power density and longer life-time compared to batteries. For some applications supercapacitors are more suitable than batteries. They can also be used to complement batteries in order to extend a battery's life-time. The use of supercapacitors is, however, still limited due to their high costs. Most commercially available supercapacitors contain expensive electrolytes and costly electrode materials. In this thesis I will present the concept of cost efficient, paper-based supercapacitors. The idea is to produce supercapacitors with low-cost, green materials and inexpensive production processes. We show that supercapacitor electrodes can be produced by coating graphite on paper. Roll-to-roll techniques known from the paper industry can be employed to facilitate an economic large-scale production. We investigated the influence of paper on the supercapacitor's performance and discussed its role as passive component. Furthermore, we used chemically reduced graphite oxide (CRGO) and a CRGO-gold nanoparticle composite to produce electrodes for supercapacitors. The highest specific capacitance was achieved with the CRGO-gold nanoparticle electrodes. However, materials produced by chemical synthesis and intercalation of nanoparticles are too costly for a large-scale production of inexpensive supercapacitor electrodes. Therefore, we introduced the idea of producing graphene and similar nano-sized materials in a high-pressure homogenizer. Layered materials like graphite can be exfoliated when subjected to high shear forces. In order to form mechanical stable electrodes, binders need to be added. Nanofibrillated cellulose (NFC) can be used as binder to improve the mechanical stability of the porous electrodes. Furthermore, NFC can be prepared in a high-pressure homogenizer and we aim to produce both NFC and graphene simultaneously to obtain a NFC-graphene composite. The addition of 10% NFC in ratio to the amount of graphite, increased the supercapacitor's capacitance, enhanced the dispersion stability of homogenized graphite and improved the mechanical stability of graphite electrodes in both dry and wet conditions. Scanning electron microscope images of the electrode's cross section revealed that NFC changed the internal structure of graphite electrodes depending on the type of graphite used. Thus, we discussed the influence of NFC and the electrode structure on the capacitance of supercapacitors.

In this thesis, two MFC based films Carboxymethylated-Microfibrillated Cellulose (MFC) and Enzymatic-MFC were characterized and metalized in order to improve the barrier properties at high relative humidity. Several methods were used for the characterization process, which were Atomic Force Microscopy (AFM), Contact Angle (CA), Energy Dispersive Spectra (EDS), Light Microscopy (LM), Scanning Electron Microscopy (SEM), and Oxygen Transmission Rate (OTR). Physical Vapor Deposition (PVD) system was used for the metalization of film, a thin layer of aluminium with a thickness of 200 nm was deposited on the films. The results revealed that ENZ-MFC exhibit a higher roughness and lower OTR values, compared to CM-MFC. The contact angle values proved that both non-metalized MFC films exhibited a hydrophilic surface with values around 50 degrees. SEM and EDS images showed that both films exhibited surface defects with dimensions in the order of a micrometer. The best barrier improvement by metalization was achieved for the metalized CM-MFC, where the OTR values were decreased by one order of magnitude after metalization. However, for ENZ-MFC metalization did not improve OTR at high RH. The protective layer was successfully protecting the MFC film as long as the surface roughness of the film was not too high. The limit is between 40 and 140nm (in root mean square roughness values). / I denna avhandling karakteriserades två MFC-baserade filmer Carboxymethylated-MFC och   Enzymatic-MFC som metalliserades för att förbättra barriäregenskaperna vid hög relativ fuktighet. Flera metoder har används för karaktäriseringsprocessen, vilka var Atomic Force Microscopy (AFM), Contact Angle (CA), Energy Dispersive Spectra (EDS), Light Microscopy (LM), Scanning Electron Microscopy (SEM), och Oxygen Transmission Rate (OTR). Physical Vapor Deposition (PVD) systemet användes för metalliseringen av filmerna, där ett tunt skikt aluminium med en tjocklek av 200 nm deponerades. Resultaten visade att ENZ-MFC har högreråhet och lägre OTR-värden jämfört med CM-MFC. Kontaktvinkelvärdena påvisade att bådaicke-metalliserade MFC-filmer har en hydrofil yta med värden omkring 50 grader. SEM- och EDS-bilder visade att båda filmerna har ytdefekter i storleksordningen en mikrometer. Den bästa barriärförbättringen genom metallisering uppnåddes för den metalliserade CM-MFC, där OTR-värdena minskade med en storleksordning efter metallisering. För ENZ-MFCförbättrade dock metallisering inte OTR vid hög RH. Det skyddande skiktet skyddar effektivt MFC-filmen så länge som filmens ytråhet inte var för hög. Gränsen är intervallet mellan 40 och140 nm (Kvadratiskt medelvärde för ytråhet).

QC 20120613

Gegenstand dieser Arbeit ist die Entwicklung funktionalisierter Cellulose-Tiefenfilterschichten. Dazu werden kommerzielle Kationenaustauscher in einer Kugelmühle nass zerkleinert und bei der Herstellung in die Tiefenfilterschichten eingebettet. Die mechanischen Eigenschaften und das Filtrationsverhalten dieser Schichten sind vergleichbar mit kommerziellen Produkten. Der maximale, technisch einsetzbare Masseanteil an Ionenaustauscher beträgt dabei ca. 40 %. In Durchströmungsversuchen wird die Funktion der eigesetzten Partikel innerhalb der Cellulose-Matrix untersucht. Die Adsorptionskinetik kann mit Hilfe eines in der Arbeit weiterentwickelten Modells nach Langmuir beschrieben werden. Für die Austauschkinetik wird auf der Basis dieses Modells eine abweichende Gesetzmäßigkeit ermittelt. Zudem wird eine Anlagen-Auslegung zur maximalen Kapazitätsausnutzung für einen Adsorptionsprozess vorgestellt.

Abstract The wood industries to this day use almost exclusively petroleum derived adhesives that are based mainly on the reaction of formaldehyde with urea, melamine or phenol. These adhesives have low cost and good adjustable properties which makes it hard for bio-based alternatives to compete. Phenol formaldehyde (PF), as an example of a synthetic adhesive, has been in use for over 100 years. In some parts of the world, legislation around formaldehyde is changing, and there is an increasingly voluntary awareness about the toxicity and unsustainability of formaldehyde. Industries realize that raw materials from oil is unstainable. The latter is currently a driving factor behind research on alternatives to amino based adhesives. Also, consumer interest in healthy and sustainable products, such as emitting less formaldehyde indoors, increases the need for bio based adhesives. Cellulose contained in plant cell walls is a renewable, abundant and nontoxic resource. During the last decades, many innovations have been achieved around cellulose and this trend does not seem to be slowing down. Cellulose shows excellent mechanical properties, high strength, high elastic modulus as well as having a low density. Research about cellulose reinforced adhesives has been increased the last years. This thesis studied the enhancement of phenol formaldehyde adhesive with Crystalline Nano Cellulose (CNC) at 5wt% and 10wt% loading levels for producing plywood boards. Indecisive results when using CNC higher than 3wt%, especially with PF resin, have been reported by other authors. In this thesis, European standards were applied. EN 314 was applied to test the panels shear strength. Three (3) treatment classes were selected, indoor room condition as well as pre-treatments 5.1.1 and 5.1.3. Other properties measured were modulus of elasticity, thickness swelling, formaldehyde emissions. Results showed a shear strength increase for all pre-treatment classes. 10wt% CNC mixture with phenol formaldehyde in water bath, pre-treatment (5.1.1) for 24h showed the highest increase in shear strength (+73,9%). The 10 wt% CNC mixture panels also showed the highest wood fibre failure of all panel types produced. A decrease in MOE has been observed with 10 wt% CNC compared to the 5 wt% CNC panels. Formaldehyde emissions tests were inconclusive, but since less PF was used, there was a general reduction in emissions. The 5 wt% CNC panels were superior in terms of modulus of elasticity and swelling and also showed improved shear strength.

Gegenstand dieser Arbeit ist die Entwicklung funktionalisierter Cellulose-Tiefenfilterschichten. Dazu werden kommerzielle Kationenaustauscher in einer Kugelmühle nass zerkleinert und bei der Herstellung in die Tiefenfilterschichten eingebettet. Die mechanischen Eigenschaften und das Filtrationsverhalten dieser Schichten sind vergleichbar mit kommerziellen Produkten. Der maximale, technisch einsetzbare Masseanteil an Ionenaustauscher beträgt dabei ca. 40 %. In Durchströmungsversuchen wird die Funktion der eigesetzten Partikel innerhalb der Cellulose-Matrix untersucht. Die Adsorptionskinetik kann mit Hilfe eines in der Arbeit weiterentwickelten Modells nach Langmuir beschrieben werden. Für die Austauschkinetik wird auf der Basis dieses Modells eine abweichende Gesetzmäßigkeit ermittelt. Zudem wird eine Anlagen-Auslegung zur maximalen Kapazitätsausnutzung für einen Adsorptionsprozess vorgestellt.

It was found that a significant improvement of mechanical properties of CFRPs can be achieved by the adjustment of the matrix properties such as toughness and CF/matrix adhesion via the chemical modification, as well as the physical modification by a small amount of cheap and environment-friendly nano fibers. Based on investigation of fracture mechanisms at macro/micro scale, the effects of matrix properties and nano fiber on the mechanical properties of CFRP have been discussed. Subsequently, the relationship has been characterized by a numerical model to show how to modulate the parameters of the matrix properties to achieve excellent fatigue properties of CFRP. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University