A novel three-layer anode having the composition Ti/TiHx/Ni-Sb-SnO2 (Ti/TiHx/NATO) was successfully prepared by a spin-coating and pyrolysis process aiming at a long service lifetime and good electrocatalytic properties for ozone formation. The TiHx as an interlayer was produced by electrochemical cathodic reduction of a coated layer of the TiOx on the titanium substrate. Spin coating and thermal decomposition were used to deposit the Sn-Sb-Ni precursor on the surface of the prepared Ti/TiHx electrode. Cyclic and linear scanning voltammetry, Raman spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to reveal the electrode performance and morphology. Results show that the onset potential for the oxygen evolution reaction (OER) of Ti/TiHx /NATO is higher than for Ti/NATO. They also indicate that the service lifetime of the Ti/TiHx/NATO is twice as long as the Ti/NATO at a current density of 50 mA.cm(-2) at room temperature. Electrochemical ozone generation and degradation of the methylene blue were investigated to confirm selectivity and activity of the electrodes. After 5 min electrolysis, a current efficiency for ozone generation of 56% was obtained the electrode with TiHx while 38% was obtained on Ti/NATO under same conditions. The results also confirm that the Ti/TiH x /NATO has a higher kinetic rate constant and decolorization efficiency for removal of the methylene blue compare to the Ti/NATO. The rate constant for the pseudo-first ordered reaction of methylene blue degradation showed high values of 350 x 10(-3) min(-1) for Ti/NATO and 440 x 10(-3) min(-1) for Ti/TiHx/NATO.
To understand how different design solutions affect users, designers traditionally use different evaluation methods that mainly rely on conscious feedback from the users. However, the complexity of human behaviour, where a large part is unconscious, point to a need for an extended tool box addressing the part not accessible to human conscious knowledge. Here, we describe a design research lab where traditional methods are complemented with tools to measure physiological signals influenced by emotional and sympathetic responses. These tools include galvanic skin response (GSR), electrocardiograph (ECG), and electroencephalograph (EEG). Typical sessions with acquired data of conscious and unconscious user reactions are described. The large body of data collected, which also require non-design expertise for interpretation, suggest that a further development towards simplified output data of the unconscious reactions is needed to allow wider use within industrial design work.
Många amputerade upplever att deras protessystem inte är lika anpassningsbara som de hoppats på. Dagens protessystem är utformade med låsta komponenter vilket begränsar användarens möjlighet att anpassa systemen till specifika ändamål. Därför påbörjades ett projekt med målet att undersöka om det finns möjlighet att skapa en snabbkoppling till protessystem genom att framställa ett konstruktionsförslag av ett lösningsalternativ. I starten av projektet påbörjades en problemformulering för att undersöka om problemen uppvisade några beroenden eller påverkade andra poster inom det framställda flödesschemat. Efter genomförd problemformulering påbörjades förstudierna för att samla in relevant information till genomförandet av projektet, där förstudien genomfördes med hjälp av en konkurrensanalys, funktionsanalys och enkätundersökning. Efter att förstudien var avklarad påbörjades en designprocess för att framställa ett konstruktionsförslag av ett lösningsförslag. Under designprocessens start formulerades en kravspecifikation så att konstruktionsförslaget hade något att förhålla sig till, och sedan påbörjades modelleringen av ett konstruktionsförslag med hjälp av Solidworks. En prototyp framställdes i plast med hjälp av en 3D- printer för att kontrollera passform av ingående komponenter och slutligen så undersöktes konstruktionsförslagets hållfasthet i Solidworks med hjälp av hållfasthetssimuleringar. Genomförandet av projektet har resulterat i en framställning av konstruktionsmaterial, prototyp, konstruktionsritningar till ett konstruktionsförslag av en snabbkoppling till protessystem. Konstruktionsförslaget kallat Hydra Coupler förser protesanvändare med möjligheten att enkelt byta proteskomponenter efter ändamål utan behov av externa verktyg, och Hydra Coupler kan även inneslutas av kosmetik utan att förlora funktionalitet.
Chiral molecules play a central role in our daily life and in nature, for instance the different enantiomers or diastereomers of a chiral molecule may show completely different biological activity. For this reason, it is a vital goal for synthetic chemists to design selective and efficient methodologies that allow the synthesis of the desired enantiomer. In this context, it is highly important that the concept of green chemistry is considered while designing new approaches that eventually will provide more environmental and sustainable chemical synthesis.The aim of this thesis is to develop the concept of combining transition metal catalysis and aminocatalysis in one process (dual catalysis). This strategy would give access to powerful tools to promote reactions that were not successful with either transition metal catalyst or the organocatalyst alone. The protocols presented in this thesis based on organocatalytic transformations via enamine or iminium intermediates or both, in combination with transition metal catalysis, describes new enantioselective organocatalytic procedures that afford valuable compounds with high chemo- and enantioselectivity from inexpensive commercial available starting materials. In paper I, we present a successful example of dual catalysis: the combination of transition metal activation of an electrophile and aminocatalyst activation of a nucleophile via enamine intermediate. In paper II, the opposite scenario is presented, here the transition metal activates the nucleophile and the aminocatalyst activates the electrophile via an iminium intermediate. In paper III,we present a domino Michael/carbocyclisation reaction that is catalysed by a chiral amine (via iminium/enamine activation) in combination with a transition metal catalysts activation of an electrophile. In paper IV, the concept of dual catalysis was further extended and applied for the highly enantioselective synthesis of valuable structural scaffolds, namely poly-substituted spirocyclic oxindoles. Finally, in paper V the concept of dual catalysis was expanded, by investigating more challenging and environmentally benign processes, such as the successful combination of a heterogeneous palladium and amine catalysts for the highly enantioselective synthesis of functionalised cyclopentenes, containing an all carbonquaternary stereocenter, dihydrofurans and dihydropyrrolidines.
This study describes a novel sustainable concept for the scalable direct fabrication and functionalization of nanocellulose from wood pulp with reduced energy consumption. A central concept is the use of metal-free small organic molecules as mediators and catalysts for the production and subsequent versatile surface engineering of the cellulosic nanomaterials via organocatalysis and click chemistry. Here, “organoclick” chemistry enables the selective functionalization of nanocelluloses with different organic molecules as well as the binding of palladium ions or nanoparticles. The nanocellulosic material is also shown to function as a sustainable support for heterogeneous catalysis in modern organic synthesis (e.g., Suzuki cross-coupling transformations in water). The reported strategy not only addresses obstacles and challenges for the future utilization of nanocellulose (e.g., low moisture resistance, the need for green chemistry, and energy-intensive production) but also enables new applications for nanocellulosic materials in different areas.
The cooperation and interplay between organic and metal catalyst Arninocatalysis systems is of utmost importance in nature and chemical synthesis. Here innovative and selective cooperative catalyst systems can be designed by combining two catalysts that complement rather than inhibit one another. This refined strategy can permit chemical transformations unmanageable by either of the catalysts alone. This review summarizes innovations and developments in selective organic synthesis that have used cooperative dual catalysis by combining simple aminocatalysts with metal catalysts. Considerable efforts have been devoted to this fruitful field. This emerging area employs the different activation modes of amine and metal catalysts as a platform to address challenging reactions. Here, aminocatalysis (e.g., enamine activation catalysis, iminium activation catalysis, single occupied molecular orbital (SOMO) activation catalysis, and photoredox activation catalysis) is employed to activate unreactive carbonyl substrates. The transition metal catalyst complements by activating a variety of substrates through a range of interactions (e.g., electrophilic pi-allyl complex formation, Lewis acid activation, allenylidene complex formation, photoredox activation, C-H activation, etc.), and thereby novel concepts within catalysis are created. The inclusion of heterogeneous catalysis strategies allows for "green" chemistry development, catalyst recyclability, and the more eco-friendly synthesis of valuable compounds.
This chapter describes the cooperative strategy of combining metal catalyst activation with aminocatalysis, with a focus on the metal acting as a Lewis acid catalyst. It gives examples where the metal catalyst promotes the reactivity of different substrates by the formation of reactive intermediates. These intermediates can act either as electrophiles or nucleophiles, which in turn can couple with nucleophilic enamine or electrophilic iminium intermediates formed between the carbonyl compounds and aminocatalyst. The chemical transformation ensues via the merging of the enamine and π‐allyl‐Pd complex via asymmetric counteranion‐direct catalysis (ACDC). Subsequently, several groups reported different co‐catalytic systems and chemical strategies for the α‐allylic alkylation of aldehydes and ketones. Cordova and coworkers reported the first example where iminium activation catalysis is combined with metal catalyst activation cooperatively. The stratagem was demonstrated for the catalytic enantioselective conjugate silyl addition to α,β‐unsaturated aldehydes.
The highly enantioselective (up to >99.5:0.5 er) synthesis of polysubstituted spirocyclic oxindoles with four new contiguous stereocenters, including the spiro all-carbon quaternary center, is disclosed. It is accomplished by the highly stereoselective control of a dynamic conjugate/intramolecular allylic alkylation relay sequence based on the synergistic cooperation of metal and chiral amine catalysts in which the careful selection of organic Nand, metal complex, and chiral amine is essential. The intermolecular C-C bond-forming step occurred only when both the metal and chiral amine catalysts were present.
We introduced an exfoliation method of MoS2 in a 3% solution of sodium dodecyl surfactant at high concentration (i.e. 2 g/L). The bulk MoS2 was thinned by mechanical exfoliation between sand papers and the resulting powder was used to prepare dispersions by liquid exfoliation through probe sonication. The resulting dispersion consisted of very thin MoS2 nanosheets in surfactant solution with average lateral size around 126 nm. This may be interesting for applications in inkjet printed electronics.
High-porosity, three-dimensional wood fiber networks made by foam forming present experimentally accessible instances of hierarchically structured, athermal fiber networks. We investigate the large deformation compression behavior of these networks using fiber-resolved finite element analyses to elucidate the role of microstructures in the mechanical response to compression. Three-dimensional network structures are acquired using micro-computed tomography and subsequent skeletonization into a Euclidean graph representation. By using a fitting procedure to the geometrical graph data, we are able to identify nine independent statistical parameters needed for the regeneration of artificial networks with the observed statistics. The compression response of these artificially generated networks and the physical network is then investigated using implicit finite element analysis. A direct comparison of the simulation results from the reconstructed and artificial network reveals remarkable differences already in the elastic region. These can neither be fully explained by density scaling, the size effect nor the boundary conditions. The only factor which provides the consistent explanation of the observed difference is the density and fiber orientation nonuniformities; these contribute to strain-localization so that the network becomes more compliant than expected for statistically uniform microstructures. We also demonstrate that the experimentally manifested strain-stiffening of such networks is due to development of new inter-fiber contacts during compression.
The sustainable improvement of the strength properties of chemimechanical pulp by eco-friendlycatalysis is disclosed. Significant research activities have been performed on the use of cationic starchand polyelectrolyte complexes for improving the strength properties of cellulose-based materials. Herewe apply an eco-friendly strategy based on catalysis for significantly improving the strength propertiesof sheets made from chemimechanical pulp (CTMP) and bleeched sulphite pulp (BSP) using sustainablepolyelectrolyte complexes as the strength additives and organocatalysis. This surface engineeringstrategy significantly increased the strength properties of the assembled sheets (up to 100% in the caseof Z-strength). We also developed a catalytic selective colour marking of the cationic potato starch (CS)and carboxymethylcellulose (CMC) in order to elucidated how the specific strength additives aredistributed on the sheets. It revealed that the strength additives were more evenly distributed on thesheets made from CTMP as compared to BSP sheets. This is most likely attributed to the presence oflignin in the former lignocellulosic material. It also contributes to the increase in strength (up to 100%,Z-strength) for the CTMP derived sheets. The selective colour marking method also revealed that morestrength additives had been bound to the pulps in the presence of the catalyst.
This work aims the functionalization of reduced graphene oxide nanoplatelets with chitosan (G-chitosan) and also with poly(styrenesulfonic acid) (GPSS), thus forming stable, dispersed aqueous solutions. G-chitosan and GPSS solutions allowed the layer-by-layer (LbL) film formation with glucose oxidase (GOx), establishing multilayered nanostructures with elevated control in thickness and morphology. The graphene nanoplatelets were characterized by UV-vis and FTIR spectroscopies, resulting in good adherence and linear deposition of the graphene nanoplatelets with GOx in the LbL structures.Cyclic voltammetry shows an enlargement in the current intensity with increasing number of deposited LbL layers, possibly owing to the formation of conducting paths by the graphene nanoplatelets in the tailored multilayer nanomaterial formed
Arabidopsis thaliana serves as a model organism for the study of fundamental physiological, cellular, and molecular processes. It has also greatly advanced our understanding of intraspecific genome variation. We present a detailed map of variation in 1,135 high-quality re-sequenced natural inbred lines representing the native Eurasian and North African range and recently colonized North America. We identify relict populations that continue to inhabit ancestral habitats, primarily in the Iberian Peninsula. They have mixed with a lineage that has spread to northern latitudes from an unknown glacial refugium and is now found in a much broader spectrum of habitats. Insights into the history of the species and the fine-scale distribution of genetic diversity provide the basis for full exploitation of A. thaliana natural variation through integration of genomes and epigenomes with molecular and non-molecular phenotypes.
The total synthesis of capsaicin analogues was performed in one pot, starting from compounds that can be derived from lignin. Heterogeneous palladium nanoparticles were used to oxidise alcohols to aldehydes, which were further converted to amines by an enzyme cascade system, including an amine transaminase. It was shown that the palladium catalyst and the enzyme cascade system could be successfully combined in the same pot for conversion of alcohols to amines without any purification of intermediates. The intermediate vanillyl-amine, prepared with the enzyme cascade system, could be further converted to capsaicin analogues without any purification using either fatty acids and a lipase, or Schotten-Baumann conditions, in the same pot. An aldol compound (a simple lignin model) could also be used as starting material for the synthesis of capsaicin analogues. Using l-alanine as organocatalyst, vanillin could be obtained by a retro-aldol reaction. This could be combined with the enzyme cascade system to convert the aldol compound to vanillylamine in a one-step one-pot reaction.
Thin inkjet-printed tracks of silver nanoparticles have previously been observed to show a non-reversible decrease in resistance when exposed to a high degree of relative humidity and thus providing sensor functionality with a memory effect. This paper provides a more in-depth explanation of the observed humidity sensor effect that originates from inkjet-printed silver nanoparticle sensors on a paper substrate. It is shown that the geometry of the sensor has a large effect on the sensor's initial resistance, and therefore also on the sensor's resistive dynamic range. The importance of the sensor geometry is believed to be due to the amount of solvent from the ink interacting with the coating of the paper substrate, which in turn enables the diffusion of salts from the paper coating into the ink and thus affecting the silver ink.
Printed electronics is a rapidly developing field where many components can already be manufactured on flexible substrates by printing or by other high speed manufacturing methods. However, the functionality of even the most inexpensive microcontroller or other integrated circuit is, at the present time and for the foreseeable future, out of reach by means of fully printed components. Therefore, it is of interest to investigate hybrid printed electronics, where regular electrical components are mounted on flexible substrates to achieve high functionality at a low cost. Moreover, the use of paper as a substrate for printed electronics is of growing interest because it is an environmentally friendly and renewable material and is, additionally, the main material used for many packages in which electronics functionalities could be integrated. One of the challenges for such hybrid printed electronics is the mounting of the components and the interconnection between layers on flexible substrates with printed conductive tracks that should provide as low a resistance as possible while still being able to be used in a high speed manufacturing process. In this article, several conductive adhesives are evaluated as well as soldering for mounting surface mounted components on a paper circuit board with inkjet printed tracks and, in addition, a double sided Arduino compatible circuit board is manufactured and programmed.
The resistance of inkjet printed lines using a silver nanoparticle based ink can be very dependent on the substrate. A very large difference in resistivity was observed for tracks printed on paper substrates with aluminum oxide based coatings compared to silica based coatings. Silica based coatings are often cationized with polymers using chloride as a counter ion. It is suggested that the precipitation of silver salts is the cause of the high resistivity, since papers pretreated with salt solutions containing ions that precipitate silver salts gave a high resistance. Silver nitrate has a high solubility and paper pretreated with nitrate ions gave a low resistivity without sintering. The results obtained show that, by choosing the correct type of paper substrate, it is possible to manufacture printed structures, such as interconnects on paper, without the need for, or at least to reduce the need for, post-print sintering. This phenomenon is, of course, ink specific. Inks without or with a low silver ion content are not expected to behave in this manner. In some sensor applications, a high resistivity is desired and, by using the correct combination of ink and paper, these types of sensors can be facilitated.
In this paper an ink-jet printed write once read many (WORM) resistive memory fabricated on paper substrate is presented. The memory elements are programmed for different resistance states by printing triethylene glycol monoethyl ether on the substrate before the actual memory element is printed using silver nano particle ink. The resistance is thus able to be set to a broad range of values without changing the geometry of the elements. A memory card consisting of 16 elements is manufactured for which the elements are each programmed to one of four defined logic levels, providing a total of 4294 967 296 unique possible combinations. Using a readout circuit, originally developed for resistive sensors to avoid crosstalk between elements, a memory card reader is manufactured that is able to read the values of the memory card and transfer the data to a PC. Such printed memory cards can be used in various applications.
Förstudien syftar till att tillsammans med MittSverige Vatten & Avfall (MSVA) ta fram verktyg för att informera om vinsterna med källsortering och påverka för att nå en bättre, mer hållbar avfallshantering i Sundsvall. En hållbar avfallshantering bidrar till att ge förutsättningar för en hållbartillväxt och god livsmiljö i Sundsvall. I förstudien presenteras exempel och förslag på hur visualiseringar kan bidra till att förbättra avfallshanteringen i Sundsvalls kommun. Inom ramen för studien har också en Återbruksfestival genomförts i syfte att undersöka och uppmärksamma vad som slängs samt ge konkreta exempel på återvinning och återbruk. Vidare genomfördes ett seminarium baserat på underliggande arbete kring hur papper och kartong kan användas som material för att ersätta hushållsförpackningar i plast. Förstudien utgör också en del i arbetet mot visionen att initiera forskning i samverkan med de aktörer i regionen som kan se nytta av design och visualisering i sin egen verksamhet. Förstudien har också bidragit till att ge underlag för framtida inriktningar, förutsättningar, och forskningsfrågor inom visualisering och design.
Today’s society is currently performing an exit from fossilfuel energy sources. The change to sustainable alternativesrequires inexpensive and environmentally friendly energy storagedevices. However, most current devices contain expensive,rare or toxic materials. These materials must be replaced bylow-cost, abundant, nontoxic components.In this thesis, I suggest the production of paper-based electricdouble-layer capacitors (EDLCs) to meet the demand oflow-cost energy storage devices that provide high power density.To fulfill the requirements of sustainable and environmentallyfriendly devices, production of EDLCs that consist of paper,graphite and saltwater is proposed. Paper can be used as aseparator between the electrodes and as a substrate for theelectrodes. Graphite is suited for use as an active material in theelectrodes, and saltwater can be employed as an electrolyte.Westudied and developed different methods for the productionof nanographite and graphene from graphite. Composites containingthese materials and similar advanced carbon materialshave been tested as electrode materials in EDLCs. I suggest theuse of cellulose nanofibers (CNFs) or microfibrillated cellulose(MFC) as a binder in the electrodes. In addition to improvedmechanical stability, the nanocellulose improved the stabilityof graphite dispersions and the electrical performance of theelectrodes. The influence of the cellulose quality on the electricalproperties of the electrodes and EDLCs was investigated.The results showed that the finest nanocellulose quality is notthe best choice for EDLC electrodes; MFC is recommended forthis application instead. The results also demonstrated thatthe capacitance of EDLCs can be increased if the electrodemasses are adjusted according to the size of the electrolyte ions.Moreover, we investigated the issue of high contact resistancesat the interface between porous carbon electrodes and metalcurrent collectors. To reduce the contact resistance, graphitefoil can be used as a current collector instead of metal foils.Using the suggested low-cost materials, production methodsand conceptual improvements, it is possible to reduce the material costs by more than 90% in comparison with commercialunits. This confirms that paper-based EDLCs are apromising alternative to conventional EDLCs. Our findings andadditional research can be expected to substantially supportthe design and commercialization of sustainable EDLCs andother green energy technologies.
Supercapacitors are high performance energy storage devices that offer many advantages like high power densities, fast charge/discharge times and long lifetimes. Due to high purchase prices the use of supercapacitors is limited. Thus we introduced the concept of low cost paper-based supercapacitors. Paper serves as a carrier for the active electrode material, as ion conductor and as separator in the supercapacitor. Different carbon materials, like graphene, graphite and activated carbon are used as active material for the electrodes. We are developing a process to produce large quantities of inexpensive graphene by mechanical exfoliation of graphite. Both coated and filled electrode papers were prepared and tested in supercapacitors. Besides graphene we coated several graphene/graphite composites on paper. By adding small amounts of gold nanoparticles or nanofibrillated cellulose (NFC) the supercapacitors performance can be improved to a great extent. Specific capacitances of up to 100 F/g for coated paper electrodes and sheet-resistances as low as 0.5 Ω/sq could be obtained. Another advantage of this concept is that papermaking technologies can be used to prepare conducting electrodes, thin separators and manufacture the device itself. The paper industry has the ability to facilitate a large scale production of inexpensive supercapacitors.
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.
Supercapacitor electrodes are often made of porous carbon materials such as activated carbon, but also graphene was frequently used as active electrode material. Graphene can be produced by mechanical exfoliation, chemical exfoliation, chemical vapor deposition or other elaborate methods. These techniques are relatively expensive and produce small quantities only. Recently we presented a method to produce nanographite and graphene by mechanical exfoliation of graphite in a high-pressure homogenizer. In our contribution “Large-scale production of graphene” by Nicklas Blomquist we suggest to optimize the geometry of the shear zone and increase the feeding pressure to obtain a higher yield.
In this study we evaluated the influence of these process optimizations on the structural and electrical properties of the nanographite-graphene mixture. The produced dispersions were characterized in terms of particle size and shape by using a particle size analyzer, a transmission electron microscope (TEM) and an atomic force microscope (AFM). In order to analyze the performance of the produced material as electrodes for supercapacitors, electrodes were produced by vacuum filtration. The electrodes were studied by sheet-resistance and capacitance measurements. Furthermore, the structure of the electrode surface and the cross section of the electrode were visualized by using a scanning electron microscope (SEM).
Comparisons with previously produced nanographite-graphene dispersions showed an increase in yield of the exfoliated nanomaterials. The optimized shear zone increased the production of nanosized particles and flakes and enhanced the material quality.
Cellulose derivatives are widely used as binders and dispersing agents in different applications. Binders composed of cellulose are an environmentally friendly alternative to oil-based polymer binding agents. Previously, we reported the use of cellulose nanofibers (CNFs) as binders in electrodes for electric double-layer capacitors (EDLCs). In addition to good mechanical stability, we demonstrated that CNFs enhanced the electrical performance of the electrodes. However, cellulose fibers can cover a broad range of length scales, and the quality requirements from an electrode perspective have not been thoroughly investigated. To evaluate the influence of fiber quality on electrode properties, we tested seven samples with different fiber dimensions that are based on the same kraft pulp. To capture the length scale from fibers to nanofibrils, we evaluated the performance of the untreated kraft pulp, refined fibers, microfibrillated cellulose (MFC) and CNFs. Electrodes with kraft pulp or refined fibers showed the lowest electrical resistivity. The specific capacitances of all EDLCs were surprisingly similar, but slightly lower for the EDLC with CNFs. The same electrode sample with CNFs also showed a slightly higher equivalent series resistance (ESR), compared to those of the other EDLCs. Graphite dispersions with MFC showed the best dispersion stability.
Symmetric electric double-layer capacitors (EDLCs) have equal masses of the same active material in both electrodes. However, having equal electrode masses may prevent the EDLC to have the largest possible specific capacitance if the sizes of the hydrated anions and cations in the electrolyte differ because the electrodes and the electrolyte may not be completely utilized. Here we demonstrate how this issue can be resolved by mass balancing. If the electrode masses are adjusted according to the size of the ions, one can easily increase an EDLC's specific capacitance. To that end, we performed galvanostatic cycling to measure the capacitances of symmetric EDLCs with different electrode mass ratios using four aqueous electrolytes-Na2SO4, H2SO4, NaOH, and KOH (all with a concentration of 1 M)-and compared these to the theoretical optimal electrode mass ratio that we calculated using the sizes of the hydrated ions. Both the theoretical and experimental values revealed lower-than-1 optimal electrode ratios for all electrolytes except KOH. The largest increase in capacitance was obtained for EDLCs with NaOH as electrolyte. Specifically, we demonstrate an increase of the specific capacitance by 8.6% by adjusting the electrode mass ratio from 1 to 0.86. Our findings demonstrate that electrode mass balancing is a simple and inexpensive method to increase the capacitance of EDLCs. Furthermore, our results imply that one can reduce the amount of unused material in EDLCs and thus decrease their weight, volume and cost.
Graphene and porous carbon materials are widely used as electrodes in supercapacitors. In order to form mechanically stable electrodes, binders can be added to the conducting electrode material. However, most bindersdegrade the electrical performance of the electrodes. Here we show that by using nanofibrillated cellulose(NFC) as binder the electrical properties, such as capacitance, were enhanced. The highest capacitance was measured at a NFC content of approximately 10% in ratio to the total amount of active material. NFC is a good ionconductor and improves the access of ions in the electrodes. Thus, electrodes made of a mixture of nanographite and NFC achieved larger capacitances in supercapacitors than electrodes with nanographite only. In addition to electrical properties, NFC enhanced the mechanical stability and wet strength of the electrodes significantly. Furthermore, NFC stabilized the aqueous nanographite dispersions, which improved the processability. Galvanostatic cycling was performed and an initial transient behaviour of the supercapacitors during the first cycles was observed. However, stabilized supercapacitors showed efficiencies of 98–100 %.
Graphene and other porous carbon materials are widely used as electrodes in supercapacitors. In order to form mechanically stable electrodes, binders can be added to the conducting electrode material. However, most binders degrade the electrical performance of the electrodes. Here we show that by using nanobrillated cellulose (NFC) as binder the electrical properties, such as sheet-resistance, were enhanced. NFC is a good ion conductor and improves the access of ions to the electrodes. Thus electrodes made of a mixture of nanographite and NFC achieved larger capacitances in supercapacitors than electrodes with nanographite only. The lowest sheet-resistance and the highest capacitance were measured at NFC contents of 10-15% in ratio to the total amount of active material. Furthermore, NFC formed a network that improved the mechanical stability of the electrodes signicantly. Beside the mechanical stability, NFC stabilized the aqueous nanographite dispersion that was used to prepare the electrodes. NFC avoids the restacking of the delaminated graphene akes by forming a ber network between the graphene layers.
Many organisms need to respond to complex, noisy environmental signals for developmental decision making. Here, we dissect how Arabidopsis plants integrate widely fluctuating field temperatures over month-long timescales to progressively upregulate VERNALIZATION INSENSITIVE3 (VIN3) and silence FLOWERING LOCUS C (FLC), aligning flowering with spring. We develop a mathematical model for vernalization that operates on multiple timescales-long term (month), short term (day), and current (hour)-and is constrained by experimental data. Our analysis demonstrates that temperature sensing is not localized to specific nodes within the FLC network. Instead, temperature sensing is broadly distributed, with each thermosensory process responding to specific features of the plants' history of exposure to warm and cold. The model accurately predicts FLC silencing in new field data, allowing us to forecast FLC expression in changing climates. We suggest that distributed thermosensing may be a general property of thermoresponsive regulatory networks in complex natural environments.
Målet med detta examensarbete var att konstruera grätzelsolceller på papper. Anledningen till att det blev papper är att det både är billigt och det finns beprövade och optimerade tillverkningsprocesser som kan användas även för pappersbaserade solceller. Grätzelceller valdes på grund av att det är den senaste generationen och är redan billigare än tidigare generationer, problemet med grätzelceller är att den än så länge inte har kommit upp i samma effektivitet som de tidigare generationerna. Komponenterna som undersöktes var anod, katod, halvledare och färgämne. För anoden testades indiumtennoxidlager (ITO) på kaptonfilm samt floriddopad tennoxidlager (FTO) på glas. Katoden var den pappersbaserade komponenten och där testades två papperssorter och en grafitfilm, den första var grafitbestryckt smörpapper och det andra var screentryckt silver på etikettpapper. De tre halvledarna som testades var alla titandioxidbaserade och de två första innehöll acetylaceton, titandioxid och triton X-100 i olika koncentrationer och den tredje innehöll vatten, titandioxid och polyvinylalkohol. Det testades två olika sorter av färgämnet och det första var björnbär och det andra var N719, som är utvecklat för grätzelceller. Resultatet blev att FTO-lagret var 1,8 gånger effektivare än ITO-lagret medan grafitfilmen gav högst effektivitet av katoderna, 2,1 gånger högre än det grafitbestrykta smörpappret men det screentryckta silveretikettspappret fungerade inte alls. Halvledaren som gav högst effektivitet var den som innehöll polymeren och var 25 respektive 1,5 gånger bättre än de andra två.
In this work we present a promising method for fabrication of conductive tracks on paper based substrates by laser assisted reduction of Graphene Oxide (GO). Printed electronics on paper based substrates is be coming more popular due to lower cost and recyclability. Fabrication of conductive tracks is of great importance where metal, carbon and polymer inks are commonly used. An emerging option is reduced graphene oxide (r-GO), which can be a good conductor. Here we have evaluated reduction of GO by using a 532 nm laser source, showing promising results with a decrease of sheet resistance from >100 M Ω/Sqr for unreduced GO down to 126 Ω/Sqr. without any observable damage to the paper substrates.
Development of printed electronics is increasing each year, where many electrical components such as transistors and sensors are now printable. The most commonly used substrate have been plastics, but there is an increasing interest in using paper as substrate. The paper industry is a very large and mature industry with large production capacity and well developed processes. It is therefore of interest to investigate how it would be possible to combine printed electronics and paper based products. This can for example be to print sensors on packages, to use large scale roll-to-roll production for solar cells. To be able to achieve such goals it is of importance to develop methods of applying electrically active materials in the large, high speed roll-to-roll processes used in the paper industry. In this article we discuss coating of graphene oxide (GO) on large areas after which it is selectively reduced into electrically conductive reduced graphene oxide (rGO) by laser processing. Graphene oxide is an inexpensive, carbon based material very suitable to be deposited as a coating, and the selective activation of makes it possible to fabricate conductive patterns at high speeds. We have evaluated several different paper substrates on which GO was coated. The reduction was performed using an 532 nm laser source and the results are promising, showing that it is possible to fabricate selectively conductive patterns on paper substrates by coating and reduction of GO.
Development of cost-effective and environmentally friendly manufacturing methods will enable important advances for the production of large-scale flexible electronics. Laser processing has shown to be a promising candidate that offers a fast and non-destructive way to produce highly conductive patterns on flexible substrates such as plastics. However, an emerging option with a lower environmental impact is instead the use of cellulose-based flexible substrates, such as paper. In this work we investigate the use of laser sintering of silver nanoparticle inks, which were inkjet-printed on three different types of paper. Patterns with a high conductivity could be manufactured where a special care was taken to prevent the substrates from damage by the intense laser light. We found that the best results was obtained for a photopaper, with a conductivity of 1.63 107 S/m corresponding to nearly 26% of the bulk silver conductivity. In addition, we demonstrate laser sintering to fabricate a fully functional near field communication tag printed on a photopaper. Our results can have an important bearing for the development of cost-effective and environmentally friendly production methods for flexible electronics on a large scale.
In this work we have investigated the use of laser sintering of different ink-jet printed nano-particle inks (NPIs) on paper substrates. Laser sintering is shown to offer a fast and non-destructive way to produce paper based printed electronics. A continuous wave fiber laser source at 1064 nm is used and evaluated in combination with a galvo-scanning mirror system. A conductivity in order of 2.16 ∗ 107 S/m is reached for the silver NPI structures corresponding to nearly 35 % conductivity compared to that of bulk silver and this is achieved without any observable damage to the paper substrate. © 2015 SPIE.
Antimicrobial resistance has reached alarming levels in many countries, thus leading to a search for new classes of antibiotics, such as antimicrobial peptides whose activity is exerted by interacting specifically with the microorganism membrane. In this study, we investigate the molecular-level mechanism of action for Labaditin (Lo), a 10-amino acid residue cyclic peptide from Jatropha multifida with known bactericidal activity againstStreptococcus mutans. We show that Lo is also effective against Staphylococcus aureus(S. aureus) but this does not apply to its linear analogue (L1). Using polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS), we observed with that the secondary structure of Lo was preserved upon interacting with Langmuir monolayers from a phospholipid mixture mimicking S. aureus membrane, in contrast to L1. This structure preservation for the rigid, cyclic Lo is key for the self-assembly of peptide nanotubes that induce pore formation in large unilamellar vesicles (LUVs), according to permeability assays and dynamic light scattering measurements. In summary, the comparison between Labaditin (Lo) and its linear analogue L1 allowed us to infer that the bactericidal activity of Lo is more related to its interaction with the membrane. It does not require specific metabolic targets, which makes cyclic peptides promising for antibiotics without bacteria resistance.
Traditional paper and papermaking have struggled with a declining market during the last decades. However, the incorporation of nanotechnology in papermaking has brought possibilities to develop low-cost, biocompatible and flexible products with sophisticated functionalities. The functionality of nanopapers emerges from the intrinsic properties of the nanofibrous network, the additional loading of specific nanomaterials, or the additional deposition and patterning of thin films of nanomaterials on the paper surface. A successful development of functional nanopapers requires understanding in how the nanopaper matrix, nanomaterial fillers, coating pigments/inks, functional additives and manufacturing processes all interact to provide the intended functionality. This review addresses the emerging area of functional nanopapers. The review discusses flexible and multifunctional nanopapers, nanomaterials being used in nanopaper making, manufacturing techniques, and functional applications that provide new important possibilities to utilize papermaking technology. The interface where nanomaterials research meets traditional papermaking has important implications for food packaging, energy harvesting, and energy storage, flexible electronics, low-cost devices for medical diagnostics, and numerous other areas.
The direct chill (DC) casting technique to produce billets for extrusion and ingots for rollingwas developed in the 1930s. The principle, which is still valid, is a two-stage cooling with a primary cooling at a mould surface followed by water spraying directly on the surface. Improvements of this technique have mainly focused on changes to the primary cooling, where a water-cooled metal mould has been replaced by different techniques to minimize cooling at this stage. The drive for development comes from the extrusion industry, which can increase the productivity and quality of extruded profiles by improving the billet surface appearance and structure. Hot top casting supported by airflow against the casting surface during the primary cooling is currently the standard procedure to achieve acceptable billet surfaces. The goal is to minimize the depth of the surface segregation zone, which is the governing factor for the appearance of different phases in the surface region. Billet surface quality is evaluated by quantifying surface appearance, segregation zone thickness, and occurrence of large Mg2Si and β-particles near the surface. The β-Al5FeSi intermetallic phase and coarse Mg2Si particles have negative effects on extrudability and workability of 6xxx Al alloys billets. To achieve extruded products with a high surface quality the as-cast billets are heat-treated before extrusion. During heat treatment the undesired intermetallic particles, i.e., β-AlFeSi platelets are transformed to rounded α-Al(FeMn)Si intermetallic phases.
In this research the formation of the surface segregation for smooth defect-free surfaces in both as-cast and homogenized billets was studied. In addition, the surfaces with defects such as wavy, spot and vertical drag defects were investigated and possible mechanisms for initiation of those defects were explained. Moreover, for a better understanding of the homogenization process in-situ studies of the heat treatment of 6082, 6005, 6060 and 6063 Al alloys were carried out by using a transmission electron microscope (TEM). Based on the observations, an explanation of the probable mechanisms taking place during transformation from β-to α-phase was presented.
During air-slip direct chill casting of aluminum alloys, uneven or low air pressure areas at the surface of the porous graphite ring mold, can cause the metal to stick to the graphite ring and produce traces along the billets called vertical drags (VD). To prevent this type of defect, it would be an advantage to decrease the wettability of the graphite ring. It has been shown that nanostructured surfaces can have hydrophobic properties, and a question is whether the same effect can be achieved for molten metals. A Ti02 nanowire structure is proposed to cover the casting ring, and the wetting behavior of such a structure has been studied, and compared to the wetting at a regular graphite ring surface by the dispensed sessile drop method. The results showed that the nanostructured surface very strongly de-wets metal droplets.
The β-Al5FeSi intermetallic phase and coarse Mg2Si particles have negative effects on extrudability and workability of 6xxx Al alloys billets. To achieve extruded products with a high surface quality, the as-cast billets are heat-treated before extrusion. During heat treatment, the undesired intermetallic particles, i.e., β-AlFeSi platelets are transformed to rounded α-Al(FeMn)Si intermetallic phases. Although the heat treatment of the bulk areas of the 6xxx Al alloys has been the focus of many previous studies, the process of phase transformation at the very surface has not been paid the same attention. In this study, microstructures of a homogenized billet of a 6082 alloy at the area very close to the surface were investigated. By comparing the X-ray diffraction patterns (XRD) of heat-treated samples as a function of different holding times, the gradual phase transformations could be followed, and using GDOES and map analysis by EDX, the alloying elemental redistribution was analyzed. Partial remelting and porosity growth was detected, and transformation rates were faster than in bulk material and from what is known from industrial processes.
During air–slip direct chill casting of aluminum alloys, uneven or low air pressure areas at the surface of the porous graphite ring mold, can cause the metal to stick to the graphite ring and produce traces along the billets called vertical drags (VD). To prevent this type of defect, it would be an advantage to decrease the wettability of the graphite ring. It has been shown that nanostructured surfaces can have hydrophobic properties, and a question is weather the same effect can be achieved for molten metals. A TiO2 nanowire structure is proposed to cover the casting ring, and the wetting behavior of such a structure has been studied, and compared to the wetting at a regular graphite ring surface by the dispensed sessile drop method. The results showed that the nanostructured surface very strongly dewetting metal droplets.
Surface defects in aluminium billet production are a real problem for the subsequent extrusion procedure. Extrusion productivity can be influenced by the surface properties, which is defined as surface appearance, surface segregation zone depth and large Mg2Si and β-particles (Al5FeSi). In this research the surface formation during DC casting of 6082 aluminium billets produced by the air slip technology is studied. The surface microstructures of 6082 aluminium alloys with smooth and wavy surface appearances were investigated, including segregation zone depths and phase formation. The results were discussed based on the exudation of liquid metal through the mushy zone. The specific appearance of the wavy surface of 6082 alloys was correlated to how the oxide skin adheres to the underlying mushy zone and coupled to the dendritic coherency and surface tension of the skin. The occurrence of different phases at the very surface and in the layer just below was explained by variations in solidification directions and subsequent segregation patterns.
The aim of this study is to increase the understanding of the surface zone formation during direct chill (DC) casting of aluminum billets produced by the air slip technology. The depth of the shell zone, with compositions deviating from the bulk, is of large importance for the subsequent extrusion productivity and quality of final products. The surface microstructures of 6060 and 6005 aluminum alloys in three different surface appearances - defect free, wavy surface, and spot defects - were studied. The surface microstructures and outer appearance, segregation depth, and phase formation were investigated for the mentioned cases. The results were discussed and explained based on the exudation of liquid metal through the mushy zone and the fact that the exudated liquid is contained within a surface oxide skin. Outward solidification in the surface layer was quantitatively analyzed, and the oxide skin movements explained meniscus line formation. Phases forming at different positions in the segregation zone were analyzed and coupled to a cellular solidification in the exudated layer.
Intermetallic β-Al5FeSi phase and coarse Mg2Si particles have negative effects on extrudability and workability of 6xxx Al alloy billets. To achieve extruded products with a high surface quality as-cast billets are therefore heat-treated before extrusion. During heat treatment the undesired intermetallic particles, i.e., β-AlFeSi platelets, are transformed to a rounded α-Al(FeMn)Si intermetallic phase. This transformation was studied in-situ by TEM for 6005 and 6082 Al alloys. It was observed that the Mg2Si particles precipitate in the Al matrix at about 250 °C; this precipitation also occurred at the edge and faces of beta intermetallic particles, and the Mg2Si particles were the preferred sites for α-Al(FeMn)Si particle nucleation. The transformation proceeded faster and at lower temperatures, 350–450 °C, than what has been reported earlier for homogenization studies of bulk samples and industrial billets. This could be associated with the thin characteristic of used samples in TEM giving contribution from fast surface diffusion, but it was also concluded that the phase boundary layer diffusion was important for the understanding of how the transformations proceed.