Indiana University-Purdue University Indianapolis (IUPUI) / For the past decade, many microfluidic paper-based analytical devices have been developed and used in different research fields. These devices are low-cost, portable, flexible, sterilizable, disposable, and easy to manufacture. The microfluidic paper-based analytical devices offer good alternatives to measurements and assays commonly performed in laboratories for analytical and clinical purposes, especially in diagnostics. In this work, we developed an electrochemical paper-based pH sensor. The determination of pH is essential in applications in areas as diverse as in the food industry, agriculture, health care or water treatment. The method presented in this work is an electroanalytical method that involves quantification of pH using stencil-painted graphite electrodes. Preliminary tests showed that pH can be determined on paper-based devices, thus indicating the presence of electroactive elements sensitive to pH on the surface of our electrodes (Chapter 4). Chemical modification of the electrode by adsorption with sodium carbonate and modification of the surface of the electrode was accomplished via: oxygen (ambient air) plasma treatment and pure oxygen plasma treatment. These treatments were to attempt to improve the definition of redox peaks on the CVs (Chapter 5). The changes made to the design of the paper-based device and the addition of a conditioning step improved the definition of the redox peaks on the CVs and increased the pH-sensing ability of our method (Chapter 6). The pH-sensing ability of our method was evaluated by testing solutions over a wide pH range. Adding sodium chloride to samples adjust the solution for accurate pH determination. The pH was successfully measured for solutions with values ranging from 1 to 13 and for artificial saliva samples prepared with pH values in the cavity-prone range (Chapter 7). This work offers a method that uses electroactive elements sensitive to pH on the surface of the PBD electrodes for pH-sensing.

Environmental issues are more and more present in our societies. Pollution engendered by plastic waste have drastically increased these past decades, causing several threats to the ecosystem. Therefore, the need of new biodegradable plastics to replace the actual petroleum-based ones is urgent. Cellulose could be a potential substitute since it is a biopolymer, abundant on Earth. However its properties have to be enhanced to be competitive towards actual plastics. The aim of the project is therefore to get a better understanding of cellulose-cellulose interactions. It focuses on the adhesion between cellulosic surfaces. Contact adhesion measurements have been performed on cellulose beads, with different treatments. All the beads had the same size and same concentration. Some of them were native whereas others were charged (600 µeq/g). Half of the native beads were surface modified with a starch coating or a Layer by Layer technique using cationic starch and an anionic polyelectrolyte (EXPN64 or FennoBond 85E). The project included preparation of the surface modified beads, pull-off tests, where load and position were recorded as a function of time, as well as measurements of the contact area. It was found that a higher energy was needed to separate charged and surface modified beads, especially the ones modified with EXPN 64, compared to native beads. The project have also shown that the types of beads influenced the contact area and the strength. However a trend was sometimes difficult to find. The data and results obtained in this project could be further re-used to enlarge the study field and investigate the influence of other parameters (size, concentration) on the adhesion of cellulose beads. / Miljöfrågor är mer och mer närvarande i våra samhällen. plastavfall har ökat drastiskt de senaste decennierna och orsakat flera hot mot ekosystemet. Därför är behovet av ny biologiskt nedbrytbar plast för att ersätta de petroleumbaserade brådskande. Cellulosa kan vara en potentiell ersättare eftersom det är en biopolymer. Emellertid måste dess egenskaper förbättras för att vara konkurrenskraftiga gentemot petroleumbaserad plast. Syftet med projektet är därför att bättre förstå cellulosa-cellulosa-interaktioner. Den fokuserar på vidhäftningen mellan cellulosaytor. Kontaktvidhäftningsmätningar har utförts på cellulosapärlor med olika behandlingar. Alla pärlor hade samma storlek och koncentration. Vissa av dem var naturliga medan andra laddades (600 µeq/g). Projektet inkluderade beredning av ytmodifierade pärlor, utdragningstester, där belastning och position registrerades som en funktion av tiden, samt mätningar av kontaktområdet. Det visade sig att högre energi behövdes för att separera laddade och ytmodifierade pärlor, särskilt de modifierade med EXPN 64, jämfört med tonativa pärlor. Projektet har också visat att typerna av pärlor påverkade kontaktområdet och styrkan. Men en trend var ibland svår att hitta. Uppgifterna och resultaten som erhållits i detta projekt kan vidare användas för att förstora studiefältet och undersöka påverkan av andra parametrar (storlek, koncentration) på vidhäftningen av cellulosapärlor.

Biodegradable polymers are emerging as a new solution to satisfy the increasing demand of greenenvironmentally friendly material. At the same time, the interest for lighter and stronger structures never stops growing. In this paper, we report the production steps to achieve cellulose nanofibrils (CNF) composite filaments via a new green synthesis route known as wet spinning. This new technique avoids the traditional harmful viscose process and produces biodegradable CNF filaments with interesting mechanical properties. This approach is then applied to produce never seen before composite CNF filaments using a three-layered head extruder. In order to obtain conductive filaments, PEDOT/PPS is successfully mixed with CNF to produce in-situ composite filaments. Scanning electron microscopy (SEM), atomic force measurements and tensile tests are employed to characterize the properties of the filaments. / Biologiskt nedbrytbara polymerer börjar framträda som en lösning för det ökade behovet avmiljövänliga material. Samtidigt så växer intresset för lättare och starkare strukturer. I denna rapport tar vi upp produktionsstegen för att uppnå nanofibril komposit cellulosa fibrer (CNF), med hjälp av en ny grön polymerisation mest känd som ”wet spinning”. Med denna nya teknik så behövs inte dem traditionella miljöfarliga viskosprocesserna och man producerar biologiskt nedbrytbara CNF filaments med intressanta mekaniska egenskaper. Denna metod appliceras sen för att producera en komposit som aldrig setts innan. CNF fibrer som består av tre lager ”head-extruder”. För att få fibrer med ledningsförmåga så mixas PEDOT/PPS med CNF för att producera ”in-situ komposit fibrer”. Svepelektronmikroskop (SEM), atomkraftsmikroskopi och töjningstester används för att karaktärisera egenskaperna av fibrerna.

Lightweight thermal paper (LWTP) is a noteworthy import commodity with wide usage and large import value in the United States. In this study, the trade pattern and market dynamics of the LWTP import market in the U.S. has been examined based on almost ideal demand system. The results revealed that both the trade volume and import source of LWTP had changed during last decade. Competition relationships were found among major suppliers in both the short run and long run, and the long-run competition is stronger than that in the short run. The repeal of restriction on conducting countervailing investigation against non-market economy temporarily stimulated the import of LWTP products from China, but the following antidumping/countervailing investigation and the corresponding punitive duties generated trade depression effect on the imports. In addition, positive trade diversion effect was found on German products, which raises doubt on the effectiveness of this trade remedy policy.

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This thesis deals with the wetting by oil mixtures of two different model cellulose surfaces. The surfaces studied were a regenerated cellulose (RG) surface prepared by spin-coating, and a film consisting of polyelectrolyte multilayers (PEM) of Poly(ethyleneimine) (PEI) and a carboxymethylated Microfibrillated Cellulose (MFC). After coating or covalently modifying the cellulose surfaces with various amounts of fluorosurfactants, the fluorinated cellulose films were used to follow the spreading mechanisms of the different oil mixtures. The viscosity and surface tension of the oil, as well as the dispersive surface energy of the cellulose surface, are essential parameters governing the spreading kinetics. X-ray Photoelectron Spectroscopy (XPS) and dispersive surface energy measurements were made on the cellulose films treated with fluorosurfactants. A strong correlation between the surface coverage of fluorine, the dispersive surface energy and the measured contact angle of the oil mixtures was found. For example, a dispersive surface energy less than 18 mN/m was required in order for the cellulose surface to be non-wetting (θe > 90º) by castor oil. Significant parts of this work were devoted to the development of cellulose surfaces for the wetting studies. The formation of a PEM consisting of PEI and MFC was studied and the total layer thickness and adsorbed amount were optimized by combining Dual Polarization Interferometry (DPI) with a Quartz Crystal Microbalance with Dissipation (QCM-D). The adsorption behaviour as well as the influence of the charge density, pH and electrolyte concentration of PEI, and electrolyte concentration of the MFC dispersion on the adsorbed amount of MFC were investigated. Results indicate that a combination of a high pH, a fairly high electrolyte concentration for PEI solution together with low or zero electrolyte concentration for the MFC resulted in the largest possible adsorbed amounts of the individual PEI and MFC layers. The structures of the two cellulose surfaces were characterised with atomic force microscopy measurements and a difference in terms of surface structure and roughness were observed. Both surfaces were however very smooth with calculated RMS roughness values in the range of a few nanometers. The adsorption behaviour of water-dispersible fluorosurfactants physically adsorbed at various concentrations onto the two model cellulose surfaces was investigated using DPI. The aggregate structure of an anionic fluorosurfactant, perfluorooctadecanoic acid, dispersed in water was studied by Cryo Transmission Electron Microscopy (Cryo-TEM). The fluorosurfactants had an adsorption and desorption behaviour in water which was dependent on the fluorinated chain length and the aggregation form of the fluorosurfactant. Perfluorooctanoic acid and a commercial cationic fluorosurfactant with a formal composition of CF3 (CF2)nSO2NH(CH2)3-4N(CH3)3+I- was found to desorb from the MFC and RG surfaces upon rinsing with water, whereas perfluorooctadecanoic acid was strongly adsorbed to the surfaces. It is essential for a fluorosurfacatant to be strongly adsorbed to the cellulose surface even after rinsing to yield hydrophobic and lipophobic (oleophobic) properties with a large contact angle for oils and water. / QC 20101103