The intrinsic mechanisms of softwood fiber damage in brown stock fiber line unit operations Lappeenranta 2010

The effects of pulp processing on softwood fiber properties strongly influence the properties of wet and dry paper webs. Pulp strength delivery studies have provided observations that much of the strength potential of long fibered pulp is lost during brown stock fiber line operations where the pulp is merely washed and transferred to the subsequent processing stages. The objective of this work was to study the intrinsic mechanisms which maycause fiber damage in the different unit operations of modern softwood brown stock processing. The work was conducted by studying the effects of industrial machinery on pulp properties with some actions of unit operations simulated in laboratory scale devices under controlled conditions. An optical imaging system was created and used to study the orientation of fibers in the internal flows during pulp fluidization in mixers and the passage of fibers through the screen openings during screening. The qualitative changes in fibers were evaluated with existing and standardized techniques. The results showed that each process stage has its characteristic effects on fiber properties: Pulp washing and mat formation in displacement washers introduced fiber deformations especially if the fibers entering the stage were intact, but it did not decrease the pulp strength properties. However, storage chests and pulp transfer after displacement washers contributed to strength deterioration. Pulp screening proved to be quite gentle, having the potential of slightly evening out fiber deformations from very deformed pulps and vice versa inflicting a marginal increase in the deformation indices if the fibers were previously intact. Pulp mixing in fluidizing industrial mixers did not have detrimental effects on pulp strength and had the potential of slightly evening out the deformations, provided that the intensity of fluidization was high enough to allow fiber orientation with the flow and that the time of mixing was short. The chemical and mechanical actions of oxygen delignification had two distinct effects on pulp properties: chemical treatment clearly reduced pulp strength with and without mechanical treatment, and the mechanical actions of process machinery introduced more conformability to pulp fibers, but did not clearly contribute to a further decrease in pulp strength. The chemical composition of fibers entering the oxygen stage was also found to affect the susceptibility of fibers to damage during oxygen delignification. Fibers with the smallest content of xylan were found to be more prone to irreversibledeformations accompanied with a lower tensile strength of the pulp. Fibers poor in glucomannan exhibited a lower fiber strength while wet after oxygen delignification as compared to the reference pulp. Pulps with the smallest lignin content on the other hand exhibited improved strength properties as compared to the references.

Uses of nitrate ion sensitive electrodes

Some models of ion-selective electrodes (ISE) and other methods have been elaborated, to quantify nitrate levels in environmental samples (water, fruits, vegetables and others), using direct potentiometry

Evaluation of gas diffusion electrodes as detectors in amperometric hydrogen sensors

This work is directed to the study and evaluation of gas diffusion electrodes as detectors in hydrogen sensors. Electrochemical experiments were carried out with rotating disk electrodes with a thin porous coating of the catalyst as a previous step to select useful parameters for the sensor. An experimental arrangement made in the laboratory that simulates the sensor was found appropriate to detect volumetric hydrogen percentages above 0.25% in mixtures H2:N2. The system shows a linear response for volumetric percentages of hydrogen between 0.25 and 2 %.

Sorption kinetics and intrapaticulate diffusivity of As(III) bioremediation from aqueous solution, using modified and unmodified coconut fiber

The pollution and toxicity problems posed by arsenic in the environment have long been established. Hence, the removal and recovery remedies have been sought, bearing in mind the efficiency, cost effectiveness and environmental friendliness of the methods employed. The sorption kinetics and intraparticulate diffusivity of As (III) bioremediation from aqueous solution using modified and unmodified coconut fiber was investigated. The amount adsorbed increased as time increased, reaching equilibrium at about 60 minutes. The kinetic studies showed that the sorption rates could be described by both pseudo-first order and pseudo-second order process with the later showing a better fit with a value of rate constant of 1.16 x 10-4 min-1 for the three adsorbent types. The mechanism of sorption was found to be particle diffusion controlled. The diffusion and boundary layer effects were also investigation. Therefore, the results show that coconut fiber, both modified and unmodified is an efficient sorbent for the removal of As (III) from industrial effluents with particle diffusion as the predominant mechanism.

Design of an adsorbent employing activated carbon fiber to remove lead

Zorflex® activated carbon fibers (ACF), reference FM100 198B, are used before and after an oxidizing procedure with H3PO4 to study the adsorption of Pb2+. The point of zero charge was determined for the modified and unmodified fiber giving values of 2.3 and 4.3, respectively. After oxidizing the ACF, the fiber showed to have a greater Pb2+ adsorption capacity in comparison with the unmodified fiber, which is related with the acid sites increase, where lead was mainly adsorbed. Determination of the BET area was carried out by nitrogen physisorption at 77K. ACFs presented superficial areas between 1000 and 1500 m²/g showing mostly, a microporous structure. The preliminary design of an adsorbent using the modified fiber is presented where the fiber superior physicochemical properties over the unmodified one are observed.

Characterization and treatment of sisal fiber residues for cement-based composite application

Sisal fiber is an important agricultural product used in the manufacture of ropes, rugs and also as a reinforcement of polymeric or cement-based composites. However, during the fiber production process a large amount of residues is generated which currently have a low potential for commercial use. The aim of this study is to characterize the agricultural residues by the production and improvement of sisal fiber, called field bush and refugo and verify the potentiality of their use in the reinforcement of cement-based composites. The residues were treated with wet-dry cycles and evaluated using tensile testing of fibers, scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. Compatibility with the cement-based matrix was evaluated through the fiber pull-out test and flexural test in composites reinforced with 2 % of sisal residues. The results indicate that the use of treated residue allows the production of composites with good mechanical properties that are superior to the traditional composites reinforced with natural sisal fibers.

Ion selective electrodes for determination of low and ultra low concentrations of lead (II) in natural waters

Att övervaka förekomsten av giftiga komponenter i naturliga vattendrag är nödvändigt för människans välmående. Eftersom halten av föroreningar i naturens ekosystem bör hållas möjligast låg, pågår en ständig jakt efter kemiska analysmetoder med allt lägre detektionsgränser. I dagens läge görs miljöanalyser med dyr och sofistikerad instrumentering som kräver mycket underhåll. Jonselektiva elektroder har flera goda egenskaper som t.ex. bärbarhet, låg energiförbrukning, och dessutom är de relativt kostnadseffektiva. Att använda jonselektiva elektroder vid miljöanalyser är möjligt om deras känslighetsområde kan utvidgas genom att sänka deras detektionsgränser. För att sänka detektionsgränsen för Pb(II)-selektiva elektroder undersöktes olika typer av jonselektiva membran som baserades på polyakrylat-kopolymerer, PVC och PbS/Ag2S. Fast-fas elektroder med membran av PbS/Ag2S är i allmänhet enklare och mer robusta än konventionella elektroder vid spårämnesanalys av joniska föroreningar. Fast-fas elektrodernas detektionsgräns sänktes i detta arbete med en nyutvecklad galvanostatisk polariseringsmetod och de kunde sedan framgångsrikt användas för kvantitativa bestämningar av bly(II)-halter i miljöprov som hade samlats in i den finska skärgården nära tidigare industriområden. Analysresultaten som erhölls med jonselektiva elektroder bekräftades med andra analytiska metoder. Att sänka detektionsgränsen m.hj.a. den nyutvecklade polariseringsmetoden möjliggör bestämning av låga och ultra-låga blyhalter som inte kunde nås med klassisk potentiometri. Den verkliga fördelen med att använda dessa blyselektiva elektroder är möjligheten att utföra mätningar i obehandlade miljöprov trots närvaron av fasta partiklar vilket inte är möjligt att göra med andra analysmetoder. Jag väntar mig att den nyutvecklade polariseringsmetoden kommer att sätta en trend i spårämnesanalys med jonselektiva elektroder.

Repair of segmental bone defects with fiber-reinforced composite: a study of material development and an animal model on rabbits

The Repair of segmental defects in load-bearing long bones is a challenging task because of the diversity of the load affecting the area; axial, bending, shearing and torsional forces all come together to test the stability/integrity of the bone. The natural biomechanical requirements for bone restorative materials include strength to withstand heavy loads, and adaptivity to conform into a biological environment without disturbing or damaging it. Fiber-reinforced composite (FRC) materials have shown promise, as metals and ceramics have been too rigid, and polymers alone are lacking in strength which is needed for restoration. The versatility of the fiber-reinforced composites also allows tailoring of the composite to meet the multitude of bone properties in the skeleton. The attachment and incorporation of a bone substitute to bone has been advanced by different surface modification methods. Most often this is achieved by the creation of surface texture, which allows bone growth, onto the substitute, creating a mechanical interlocking. Another method is to alter the chemical properties of the surface to create bonding with the bone – for example with a hydroxyapatite (HA) or a bioactive glass (BG) coating. A novel fiber-reinforced composite implant material with a porous surface was developed for bone substitution purposes in load-bearing applications. The material’s biomechanical properties were tailored with unidirectional fiber reinforcement to match the strength of cortical bone. To advance bone growth onto the material, an optimal surface porosity was created by a dissolution process, and an addition of bioactive glass to the material was explored. The effects of dissolution and orientation of the fiber reinforcement were also evaluated for bone-bonding purposes. The Biological response to the implant material was evaluated in a cell culture study to assure the safety of the materials combined. To test the material’s properties in a clinical setting, an animal model was used. A critical-size bone defect in a rabbit’s tibia was used to test the material in a load-bearing application, with short- and long-term follow-up, and a histological evaluation of the incorporation to the host bone. The biomechanical results of the study showed that the material is durable and the tailoring of the properties can be reproduced reliably. The Biological response - ex vivo - to the created surface structure favours the attachment and growth of bone cells, with the additional benefit of bioactive glass appearing on the surface. No toxic reactions to possible agents leaching from the material could be detected in the cell culture study when compared to a nontoxic control material. The mechanical interlocking was enhanced - as expected - with the porosity, whereas the reinforcing fibers protruding from the surface of the implant gave additional strength when tested in a bone-bonding model. Animal experiments verified that the material is capable of withstanding load-bearing conditions in prolonged use without breaking of the material or creating stress shielding effects to the host bone. A Histological examination verified the enhanced incorporation to host bone with an abundance of bone growth onto and over the material. This was achieved with minimal tissue reactions to a foreign body. An FRC implant with surface porosity displays potential in the field of reconstructive surgery, especially regarding large bone defects with high demands on strength and shape retention in load-bearing areas or flat bones such as facial / cranial bones. The benefits of modifying the strength of the material and adjusting the surface properties with fiber reinforcement and bone-bonding additives to meet the requirements of different bone qualities are still to be fully discovered.

Surface transformation hardening of carbon steel with high power fiber laser

This study investigated the surface hardening of steels via experimental tests using a multi-kilowatt fiber laser as the laser source. The influence of laser power and laser power density on the hardening effect was investigated. The microhardness analysis of various laser hardened steels was done. A thermodynamic model was developed to evaluate the thermal process of the surface treatment of a wide thin steel plate with a Gaussian laser beam. The effect of laser linear oscillation hardening (LLOS) of steel was examined. An as-rolled ferritic-pearlitic steel and a tempered martensitic steel with 0.37 wt% C content were hardened under various laser power levels and laser power densities. The optimum power density that produced the maximum hardness was found to be dependent on the laser power. The effect of laser power density on the produced hardness was revealed. The surface hardness, hardened depth and required laser power density were compared between the samples. Fiber laser was briefly compared with high power diode laser in hardening medium-carbon steel. Microhardness (HV0.01) test was done on seven different laser hardened steels, including rolled steel, quenched and tempered steel, soft annealed alloyed steel and conventionally through-hardened steel consisting of different carbon and alloy contents. The surface hardness and hardened depth were compared among the samples. The effect of grain size on surface hardness of ferritic-pearlitic steel and pearlitic-cementite steel was evaluated. In-grain indentation was done to measure the hardness of pearlitic and cementite structures. The macrohardness of the base material was found to be related to the microhardness of the softer phase structure. The measured microhardness values were compared with the conventional macrohardness (HV5) results. A thermodynamic model was developed to calculate the temperature cycle, Ac1 and Ac3 boundaries, homogenization time and cooling rate. The equations were numerically solved with an error of less than 10-8. The temperature distributions for various thicknesses were compared under different laser traverse speed. The lag of the was verified by experiments done on six different steels. The calculated thermal cycle and hardened depth were compared with measured data. Correction coefficients were applied to the model for AISI 4340 steel. AISI 4340 steel was hardened by laser linear oscillation hardening (LLOS). Equations were derived to calculate the overlapped width of adjacent tracks and the number of overlapped scans in the center of the scanned track. The effect of oscillation frequency on the hardened depth was investigated by microscopic evaluation and hardness measurement. The homogeneity of hardness and hardened depth with different processing parameters were investigated. The hardness profiles were compared with the results obtained with conventional single-track hardening. LLOS was proved to be well suitable for surface hardening in a relatively large rectangular area with considerable depth of hardening. Compared with conventional single-track scanning, LLOS produced notably smaller hardened depths while at 40 and 100 Hz LLOS resulted in higher hardness within a depth of about 0.6 mm.

Characterization of fiber and vessel elements in pulp suspension images

The thesis is related to the topic of image-based characterization of fibers in pulp suspension during the papermaking process. Papermaking industry is focusing on process control optimization and automatization, which makes it possible to manufacture highquality products in a resource-efficient way. Being a part of the process control, pulp suspension analysis allows to predict and modify properties of the end product. This work is a part of the tree species identification task and focuses on analysis of fiber parameters in the pulp suspension at the wet stage of paper production. The existing machine vision methods for pulp characterization were investigated, and a method exploiting direction sensitive filtering, non-maximum suppression, hysteresis thresholding, tensor voting, and curve extraction from tensor maps was developed. Application of the method to the microscopic grayscale pulp images made it possible to detect curves corresponding to fibers in the pulp image and to compute their morphological characteristics. Performance of the method was evaluated based on the manually produced ground truth data. An accuracy of fiber characteristics estimation, including length, width, and curvature, for the acacia pulp images was found to be 84, 85, and 60% correspondingly.

Carbon Nanotubes as Material for Supercapacitor Electrodes

Electrochemical double-layer supercapacitors have an intermediate position between rechargeable batteries, which can store high amounts of energy, and dielectric capacitors, which have high output power. Supercapacitors are widely suggested to be used in automobiles (recuperation during braking, facilitate engine starting, electric stabilization of the system), industry (forklifts, elevators), hybrid off-road machinery and also in consumer electronics. Supercapacitor electrodes require highly porous material. Typically, activated carbon is used. Specific surface area of activated carbon is approximately 1000 m2 per gram. Carbon nanotubes represent one of prospective materials. According to numerous studies this material allows to improve the properties of supercapacitors. The task of this Master‘s Thesis was to test multiwalled carbon nanotubes and become confident with the testing methods.

Stereological study of the elastic fiber and smooth muscle cell system in the bovine and buffalo penis

Samples of ten penises of Mediterranean buffaloes and ten penises of Red Sindhi cattle were used. The thickness of the tunica albuginea (TA), distribution of smooth muscle cells (SMC) and volume density (Vv) of elastic system fibers in TA, corpus cavernosum (CC) and corpus spongiosum (CS) were evaluated. The Vv of elastic system fibers in buffalo and bovine penis was respectively 4.07% ±0.88% and 3.36% ±1.21% in TA; 17.32% ±2.21% and 13.14% ±1.27% (CC), 26.58% ±4.31% and 31.36% ±3.67% (CS). The CC of buffalo presented higher Vv of elastic fibers than bovine, while in the CS the Vv of elastic fibers in buffaloes was smaller than in cattle. The TA thickness showed a significant difference among the species studied. The arrangement of SMC in the bovine penises and in the water buffalo suggests that this pattern is common to animals that have fibroelastic penises.

Paper for printed electronics and functionality

Mass-produced paper electronics (large area organic printed electronics on paper-based substrates, “throw-away electronics”) has the potential to introduce the use of flexible electronic applications in everyday life. While paper manufacturing and printing have a long history, they were not developed with electronic applications in mind. Modifications to paper substrates and printing processes are required in order to obtain working electronic devices. This should be done while maintaining the high throughput of conventional printing techniques and the low cost and recyclability of paper. An understanding of the interactions between the functional materials, the printing process and the substrate are required for successful manufacturing of advanced devices on paper. Based on the understanding, a recyclable, multilayer-coated paper-based substrate that combines adequate barrier and printability properties for printed electronics and sensor applications was developed in this work. In this multilayer structure, a thin top-coating consisting of mineral pigments is coated on top of a dispersion-coated barrier layer. The top-coating provides well-controlled sorption properties through controlled thickness and porosity, thus enabling optimizing the printability of functional materials. The penetration of ink solvents and functional materials stops at the barrier layer, which not only improves the performance of the functional material but also eliminates potential fiber swelling and de-bonding that can occur when the solvents are allowed to penetrate into the base paper. The multi-layer coated paper under consideration in the current work consists of a pre-coating and a smoothing layer on which the barrier layer is deposited. Coated fine paper may also be used directly as basepaper, ensuring a smooth base for the barrier layer. The top layer is thin and smooth consisting of mineral pigments such as kaolin, precipitated calcium carbonate, silica or blends of these. All the materials in the coating structure have been chosen in order to maintain the recyclability and sustainability of the substrate. The substrate can be coated in steps, sequentially layer by layer, which requires detailed understanding and tuning of the wetting properties and topography of the barrier layer versus the surface tension of the top-coating. A cost competitive method for industrial scale production is the curtain coating technique allowing extremely thin top-coatings to be applied simultaneously with a closed and sealed barrier layer. The understanding of the interactions between functional materials formulated and applied on paper as inks, makes it possible to create a paper-based substrate that can be used to manufacture printed electronics-based devices and sensors on paper. The multitude of functional materials and their complex interactions make it challenging to draw general conclusions in this topic area. Inevitably, the results become partially specific to the device chosen and the materials needed in its manufacturing. Based on the results, it is clear that for inks based on dissolved or small size functional materials, a barrier layer is beneficial and ensures the functionality of the printed material in a device. The required active barrier life time depends on the solvents or analytes used and their volatility. High aspect ratio mineral pigments, which create tortuous pathways and physical barriers within the barrier layer limit the penetration of solvents used in functional inks. The surface pore volume and pore size can be optimized for a given printing process and ink through a choice of pigment type and coating layer thickness. However, when manufacturing multilayer functional devices, such as transistors, which consist of several printed layers, compromises have to be made. E.g., while a thick and porous top-coating is preferable for printing of source and drain electrodes with a silver particle ink, a thinner and less absorbing surface is required to form a functional semiconducting layer. With the multilayer coating structure concept developed in this work, it was possible to make the paper substrate suitable for printed functionality. The possibility of printing functional devices, such as transistors, sensors and pixels in a roll-to-roll process on paper is demonstrated which may enable introducing paper for use in disposable “onetime use” or “throwaway” electronics and sensors, such as lab-on-strip devices for various analyses, consumer packages equipped with product quality sensors or remote tracking devices.

Development of porous glass-fiber reinforced composite for bone implants. Evaluation of antimicrobial effect and implant fixation

Cranial bone reconstructions are necessary for correcting large skull bone defects due to trauma, tumors, infections and craniotomies. Traditional synthetic implant materials include solid or mesh titanium, various plastics and ceramics. Recently, biostable glass-fiber reinforced composites (FRC), which are based on bifunctional methacrylate resin, were introduced as novel implant solution. FRCs were originally developed and clinically used in dental applications. As a result of further in vitro and in vivo testing, these composites were also approved for clinical use in cranial surgery. To date, reconstructions of large bone defects were performed in 35 patients. This thesis is dedicated to the development of a novel FRC-based implant for cranial reconstructions. The proposed multi-component implant consists of three main parts: (i) porous FRC structure; (ii) bioactive glass granules embedded between FRC layers and (iii) a silver-polysaccharide nanocomposite coating. The porosity of the FRC structure should allow bone ingrowth. Bioactive glass as an osteopromotive material is expected to stimulate the formation of new bone. The polysaccharide coating is expected to prevent bacterial colonization of the implant. The FRC implants developed in this study are based on the porous network of randomly-oriented E-glass fibers bound together by non-resorbable photopolymerizable methacrylate resin. These structures had a total porosity of 10–70 volume %, of which > 70% were open pores. The pore sizes > 100 μm were in the biologically-relevant range (50-400 μm), which is essential for vascularization and bone ingrowth. Bone ingrowth into these structures was simulated by imbedding of porous FRC specimens in gypsum. Results of push-out tests indicated the increase in the shear strength and fracture toughness of the interface with the increase in the total porosity of FRC specimens. The osteopromotive effect of bioactive glass is based on its dissolution in the physiological environment. Here, calcium and phosphate ions, released from the glass, precipitated on the glass surface and its proximity (the FRC) and formed bone-like apatite. The biomineralization of the FRC structure, due to the bioactive glass reactions, was studied in Simulated Body Fluid (SBF) in static and dynamic conditions. An antimicrobial, non-cytotoxic polysaccharide coating, containing silver nanoparticles, was obtained through strong electrostatic interactions with the surface of FRC. In in vitro conditions the lactose-modified chitosan (chitlac) coating showed no signs of degradation within seven days of exposure to lysozyme or one day to hydrogen peroxide (H2O2). The antimicrobial efficacy of the coating was tested against Staphylococcus aureus and Pseudomonas aeruginosa. The contact-active coating had an excellent short time antimicrobial effect. The coating neither affected the initial adhesion of microorganisms to the implant surface nor the biofilm formation after 24 h and 72 h of incubation. Silver ions released to the aqueous environment led to a reduction of bacterial growth in the culture medium.

Improvement of wet and dry web properties in papermaking by controlling water and fiber quality

Pappersindustrin står inför många utmaningar och bör uppfylla krav som ställs av t.ex. marknadstrender och slutanvändare. Snabbare och effektivare processer ställer även större krav på pappersbanans mekaniska egenskaper. Avbrott i produktionen sker inte enbart pga. låg styrka utan orsaken kan även vara en för låg spänning i pappersbanan. De flesta problemen sker vid våtpressen och/eller i början av torkpartiet då papprets torrhalt är 30-70 %. Spänningen hålls inte konstant efter töjning, utan sjunker pga. papprets relaxering, som till största delen sker då pappret flyttas från pressen till torkpartiet. Ur forskningssynvinkel öppnar en smidigt fungerande verksamhet med potentiella energibesparingar upp möjligheterna för förbättring av befintliga processer. I detta arbete undersöktes hur olika faktorer inverkar på fibernätverkets avvattning, initiala våtstyrka och relaxering samt också på slutproduktens mekaniska egenskaper och ytegenskaper. I första delen ändrades processvattnets egenskaper, såsom pH, konduktivitet och ytspänning. Ytspänningen varierades genom tillsatts av ett nonjoniskt ytaktivt ämne, s.k. surfaktant. Fiberegenskaperna modifierades också. Fibern maldes antingen genom en mild eller genom en hård process. Effekten av finmaterial undersöktes genom att tillsätta finmaterial till den ursprungliga massan eller genom att avlägsna finmaterialet från den malda massan. I den sista delen användes en hemicellulosa, som finns i stora mängder i gran, som tillsatsmedel. Förutom naturliga galaktoglukomannaner (GGM), tillverkades också en katjoniserad, en karboximetylerad samt en iminerad, amfifil GGM. Dessa användes i pappersmassa eller sprayades på ytan av ett nybildat ark. Resultaten, som erhölls i denna avhandling, bildar en värdefull kunskapsbas, som kan användas för kontroll och reglering av pappersmaskinens körbarhet och papperskvalitet.