Master of Science / Department of Grain Science & Industry / Xiuzhi Susan Sun / Bio-based protein adhesives derived from renewable resources, especially soy protein are becoming more significant due to the concerns about environment and health related issues and the limit of petroleum recourses. However, the relatively poor water resistance of soy-based protein adhesives limits its wide applications. The goal of this study was to improve the water resistance performance of soy-based protein adhesives by chemical modification. The specific objectives are 1) to modify soy protein with calcium carbonate (CaCO[subscript]3) and sodium bisulfite (NaHSO[subscript]3) as the denaturing agents; 2) to investigate the effects of calcium carbonate (CaCO[subscript]3) concentrations, curing time and curing temperatures on adhesion performance of the modified soy-based protein adhesives. In this study, the co-effects of NaHSO[subscript]3 and CaCO[subscript]3 on adhesion properties of soy protein adhesives were investigated. NaHSO[subscript]3 was added to soy flour slurry at constant concentration 6g/L, while concentration of CaCO[subscript]3 was chosen in the range of 0 to 23g/L. Soy protein adhesives modified with 4g/L and 16g/L CaCO[subscript]3 were selected to characterize the adhesion performance on 3 ply yellow pine plywood using the Response Surface Method (RSM). The effects of curing temperature and curing time on the adhesion properties were also studied. The major findings are 1) 4g/L CaCO[subscript]3, 6g/L NaHSO[subscript]3 modified soy protein adhesives (MSPA) had better adhesion performance (both dry and wet) than 16g/L CaCO[subscript]3, 6g/L NaHSO[subscript]3 MSPA; 2) Higher temperature (170°C) resulted in higher wet shear adhesion strengths; 3) Longer hot press time had positive impact on wet adhesion shear strength; and 4) 4g/L CaCO[subscript]3, 6g/L NaHSO[subscript]3 MSPA showed better adhesion shear strength after 2 weeks storage than 16g/L CaCO[subscript]3, 6g/L NaHSO[subscript]3 MSPA. In general, 4g/L CaCO[subscript]3, 6g/L NaHSO[subscript]3 MSPA, under longer hot press time and higher temperature would lead to a better adhesion performance.

Doctor of Philosophy / Department of Grain Science and Industry / X. Susan Sun / Oilseed protein is a promising renewable source to be used as the replacement of petroleum-based materials for adhesion purpose, and it has drawn increasing attention since soy-based adhesives were developed for wood glues. However, soy protein comprises a portion of humans’ diets, thereby creating competition between utilization of soy protein for protein-based products or human food. Therefore, alternative bio-resources must be discovered. Proteins from camelina sativa provide such potential. Similar to other protein-based polymers, low mechanical strength and poor water resistance are the major drawbacks limiting camelina protein’s further applications. In this research, camelina protein (CP) was modified by unfolding, crosslinking, and co-polymerization treatment for improved flow-ability, adhesion properties and water resistance, which facilitates the industrialization of camelina as an alternative to soy-based adhesives. The physicochemical properties and microstructures of CP were also investigated. To increase the reactivity of CP adhesive, the first step is to denature the folded structure of native proteins. Camelina protein was extracted from defatted camelina meal through alkali solubilization and acid precipitation and modified with varying amount of NaHSO₃ (0-12% of the protein dry base) and Gdm.Cl (0-250% of the protein dry base). NaHSO₃ treatment broke the disulfide bonds of the CP and thus increased its free sulfhydryl content and surface hydrophobicity. As NaHSO₃ concentration increased, the viscosity, elastic modulus (G') and water resistant of NaHSO₃-modified camelina protein (SMCP) dispersion decreased, and the protein became hydrophobic. Gdm.Cl treatment broke the CPI’s hydrogen bonds but decreased their surface hydrophobicity. Similarly, viscosity, G', and water resistant of Gdm.Cl-modified camelina protein (GMCP) dispersions decreased as Gdm.Cl increased and protein became to aggregate. The reducing effect of NaHSO₃ was more obvious than Gdm.Cl to disrupt CPI’s intermolecular protein interaction but less obvious than Gdm.Cl to reduce the viscosity and water resistant. To further increase the CP’s water resistance, a coupling agent, Ethyl-3-(3-dimethyl-aminopropyl-1-carbodiimide) (EDC), was applied to stabilize the protein structure by crosslinking the free carboxyl groups and amino groups. The cross-linked CP exhibited increased molecular weight and particle size. Microstructures of modified CP also became rigid and condensed. Accordingly, CP’s increased intermolecular protein interaction resulted in its higher elastic modulus, viscosity and water resistance. The ultrasound pretreatment further increased the crosslink degree of CP, which resulted in protein’s increased aggregation behaviors and compact micro-structures. Consequently, the elastic modulus, viscosity, and water resistance of CP increased accordingly. Copolymerization with hydrophobic enhancers was also an effective method to improve CP’s water resistance. In this study, kraft lignin was oxidized by H₂O₂ and then copolymerized with CP as wood adhesives, which exhibited increased wet strength. In the presence of ultrasound irradiation, the H₂O₂-depolymerized kraft lignin exhibited reduced particle size, thermal stability and increased content of hydroxyl groups. Fluorescence spectroscopy analysis revealed that after coupling with pristine or de-polymerized lignin, CP exhibited increased hydrophobicity due to lignin’s increased reactivity with camelina protein. Accordingly, the water resistance of CP-based adhesives improved. In the optimized condition, when CP was copolymerized with ultrasound-induced oxidized lignin, it had increased wet shear adhesion strength from 0.28 MPa to 1.43 MPa, with wood panels passing the three-cycle water soaking test.

119 leaves single sided printed, preliminary pages and numbered pages 1-101. Includes bibliography and a list of tables, figures, schemes and abbreviations. Digitized at 300 dpi (OCR), used Bizhub 250. / Thesis (MSc (Polymer Science))--University of Stellenbosch, 2006. / ENGLISH ABSTRACT: The properties and interactions of cellulose surfaces are of a great technical interest during papermaking and recycling. Sizing, the modification of fiber surfaces, e.g. with the purpose to reduce water penetration into the paper structure, plays an important role in obtaining paper with good printability and water resistance. Water resistance is the key end-property of paper being investigated in this study. Firstly a comparison was made between the degree of surface modification of cellulose by means of anionic, nonionic and reactive surfactants. The amount of surfactant adsorbed by the paperboard was determined and the paper surface evaluated via scanning electron microscopy (SEM). The sizing efficiency of the three industrial surfactants was evaluated in order to establish the surfactant structure best suited for sizing recycled paperboard. This was done via the Cobb test, an industrial method to measure water uptake by paper, and contact angle measurements. The reactive surfactant was found to have the best sizing efficiency and focus shifted to synthesizing selected copolymer surfactants via free radical copolymerization. Two copolymers were synthesized, with maleic anhydride as the polar part in both. Butyl methacrylate and lauryl methacrylate were selected as the hydrophobic parts in the respective copolymer systems. The unavailability of reactivity ratios for the respective copolymer systems led to the use of in situ proton nuclear magnetic resonance spectroscopy CH NMR) for the determination of the co-monomer incorporation in both copolymer systems. Quantitative 13C NMR spectroscopy was also employed in order to establish the co-monomer content of the isolated copolymers obtained during bench-scale (laboratory) experiments. Lastly, a comparison of the degree of surface modification of cellulose was made between that which was achieved with the industrial reactive surfactant and that with the two synthesized polymeric reactive surfactants. The two synthesized polymeric surfactants were found to have a better sizing efficiency than the industrial reactive surfactant, and the maleic anhydride-lauryl methacrylate copolymer system gave the best results. / AFRIKAANSE OPSOMMING: Die eienskappe en interaksies van sellulose-oppervlaktes is van groot tegniese belang gedurende die vervaardiging en hergebruik van papier. Oppervlakte behandeling, die modifikasie van vesel-oppervlaktes bv. met die doel om water indringing in die papierstruktuur te verminder, speel 'n belangrike rol in die daarstel van papier met goeie drukkwaliteit en waterweerstand. Waterweerstand is die sleuteleienskap van papier wat in hierdie werkstuk ondersoek word. Eerstens is daar 'n vergelyking getref tussen die verandering van sellulose-oppervlaktes deur middel van anioniese, nie-ioniese en reaktiewe sepe. Die hoeveelheid seep geabsorbeer deur die papierbord is bepaal en die papier-oppervlak ondersoek deur middel van skandeer-elektronmikroskopie (SEM). Die behandelingsdoeltreffendheid van die drie industriele sepe is ondersoek om vas te stel watter seep die beste struktuur het om hergebruikte papierbord effektief te behandel. Dit is gedoen deur middel van die Cobbtoets, 'n industriele metode om wateropname van papier te meet, asook kontakhoekmetings. Daar is gevind dat die reaktiewe seep die beste behandelingsdoeltreffendheid het en daar is vervolgens gekonsentreer op die bereiding van geselekteerde reaktiewe kopolimeersepe deur middel van vryeradikaalkopolimerisasie. Twee kopolimere is berei, met maleienanhidried as die polere gedeeite van albei. Butielmetakrilaat en laurielmetakrilaat is gekies vir die nie-polere gedeeltes van die onderskeie kopolimeersisteme. Die onbeskikbaarheid van reaktiwiteitsverhoudings vir die onderskeie kopolimeersisteme het gelei tot die gebruik van in situ proton kern magnetiese resonansie spektroskopie eH KMR) vir die bepaling van die ko-monomeer insluiting in beide kopolimeersisteme. Kwantitatiewe koolstofdertienkemmagnetieseresonansie spektroskopie (13C KMR) is ook gebruik om die ko-monomeerinhoud van die geisoleerde kopolimere, verkry tydens laboratoriumeksperimente, te bepaal. Laastens is 'n vergelyking getref tussen die graad van modifikasie van selluloseoppervlaktes deur middel van die industriele reaktiewe seep in vergelyking met die twee bereide polimeriese reaktiewe sepe. Daar is gevind dat die twee gesintetiseerde polimeriese sepe beter behandelingsdoeltreffendheid as die industriele reaktiewe seep het, met die maleienanhidried-laurielmetakrilaat-kopolimeersisteem wat die beste resultaat lewer.

Yes / Aluminium alloys are widely used structural materials in automotive, aerospace, and transportation, among several other notable industries. However, aluminium alloys' low hardness and poor tribological performance prevent potential use in applications requiring high contact pressures and wear resistance. This paper presents a novel two-step technique for enhancing the mechanical properties of the aluminium alloy by impregnating the surface with Ni-coating containing hard TiO2 nanoparticles using a high-intensity electric arc generated during tungsten inert gas welding. The results show that the process significantly changes the Microstructure and mechanical properties. The surface hardness increased from 0.48 GPa to 0.65 GPa with a corresponding change of Young's modulus from 15 GPa to 24 GPa of the treated surface.

The purpose of this study is to explore the practical implementation of a commercially available sustainable alternative to conventional polyurethane (PU) textile coating for functional outerwear garments with protection from rain and snow. In addition, this study will identify the key consideration areas which should be taken into account during the managerial decision-making process of implementing the sustainable PU coating. This study employed an exploratory research design which used both quantitative and qualitative research methods to support in answering the research questions. The qualitative and quantitative research methods were applied respectively through semi-structured interviews and sample development trials. The research design began with a systematic literature review (SLR), then semi-structured interviews were conducted prior to sample development, then an experimental sample development was conducted, and lastly, additional semi-structured interviews were conducted subsequent to sample development. The findings revealed that the key consideration areas which should be taken into account during the managerial decision-making process of implementing a sustainable PU coating include chemical sustainability, legislative regulations, supplier capabilities, product quality and performance, purchase price, and lead time. Water-based PU coating was identified as a viable sustainable alternative to conventional PU coating for the application on textiles. Out of the three selected chemical suppliers, chemical supplier 1 was recommended by the researchers to the collaborating Swedish fashion brand as they were successful in producing a water-based PU coating which fulfilled all performance and key consideration area requirements. This research study contributes to furthering the development of water-based PU coating in the textile and apparel industry by developing a comprehensive implementation process from a practical managerial perspective.

京都大学 / 新制・課程博士 / 博士(農学) / 甲第25018号 / 農博第2578号 / 新制||農||1103(附属図書館) / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 梅村 研二, 教授 矢野 浩之, 教授 村田 功二 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Syftet med denna studie var att utveckla en biokomposit med både fett-och vattenbarriär. Material med dessa egenskaper innehåller idag ofta PFAS-molekyler (per- och polyfluorerade alkylsubstanser). Det är av stor betydelse att byta ut dessa mot ett biobaserat alternativ då de är giftiga och ackumuleras i naturen. Biokompositen utvecklades genom att kombinera icke-trä pappersmassa (75%) och trä pappersmassa (25%) som matris. Därefter tillsattes olika biobaserade additiv i våtände för att påverka materialets egenskaper. Proverna testades på deras dragstyrka, vattenavvisning och fettavvisning. Den stora utmaningen var att lyckas med fettavisningen. 1% Polysackarid 1 tillsammans med 0.5% sizing komponent var det provet som gav bäst resultat. För att utvärdera denna metod gjordes en jämförelse med ytbehandling. Det gjordes genom att stryka på några av de tidigare använda additiven på ytan av matrisen. Ytbehandlingen visade sig ha en större påverkan på fettavvisningen men med liknande eller sämre påverkan på vattenavvisningen. Nackdelen med denna metod är att den kräver ett flertal extra steg i produktionen. / The aim of this thesis work was to develop a pulp-based biocomposite material with good water and grease barrier properties. It is important to achieve such properties to able to replace PFAS (poly- and perfluoroalkyl substances) molecules due to their toxicity and accumulation. Different types of pulp were evaluated as the matrix and the optimal matrix was based on non-wood pulp (75%) with wood pulp 1 (25%).  This was also combined with several different additives in the wet-end. The samples were tested for their tensile strength, water resistance and grease resistance. The biggest challenge was to achieve adequate grease resistance. 1% Polysaccharide 1 together with 0.5% sizing agent was one of the better samples. It was clear the additives affected each other when used in combination with each other which indicates that wet end chemistry is complex. For a comparison, some additives were also tested as coatings. This technique resulted in better grease resistance but requires several extra steps in the production.

No description available.

Darbe analizuojami laivo pasipriešinimo nustatymo būdai, metodai. Aprašomas praktiškai atliktas karinio laivo 5415 pasipriešinimo modelinis bandymas, bei pateikiami bandymo rezultatai. Naudojantis FLOW 3D simuliacine programa modeliuojamas virtualus laivo 5414 pasipriešinimo bandymas, bei pateikiami virtualaus bandymo rezultatai. Taikant daţnai naudojamus praktikoje apytikrius vandens pasipriešinimo skaičiavimo metodus vertinamas vandens pasipriešinimas laivo 5415 judėjimui. Palyginami apytikrių skaičiavimo metodų, bei realaus ir virtualaus pasipriešinimo eksperimentų rezultatai. Padaromos išvados, kaip tikslingai parinkti optimalų laivo eigumo preliminaraus vertinimo metodą laivo projektavimo metu. / The most used ship's resistance research techniques and methods were analyzed in current work. Were described war ship 5415 practical resistance modeling test and submitted test calculations. Using automation simulation program FLOW 3D were created a virtual ship resistance test and also submitted test calculations. Using approximate water resistance calculation methods was evaluated water resistance of the vessel 5415. Were compared the result of approximate resistance calculation method's, real and virtual resistance test experiment's. Were made conclusions, how to select the most optimal ship powering preliminary assessment method on the design stage.

Abstracts Cellulose nanopapers are the strongest polymeric material known to us, and in the near future, they are likely to be a backbone of numerous functional materials. Cellulose nanopapers have gained much attention due to qualities such as their environmentally friendly nature, renewable raw material source and biodegradability. Additionally, they offer an industrially adaptable, water-based processing route, which is similar to current paper production. Functionally, besides being tougher than any known plastic, cellulose nanopapers remain foldable like a paper. Despite their fascinating properties, cellulose nanopapers are still far from commercialisation – mainly due to two obstacles. Firstly, it can take up to hours to prepare a nanopaper due to poor draining of cellulosic nanofibres. Secondly, cellulose nanopapers have extremely poor water and humidity resistance, as up to 90% of their stiffness is lost in the presence of water. The purpose of this dissertation is to address both obstacles and suggest an eco-friendly yet industrially relevant solution. Two approaches are employed: increasing the hydrophobicity of cellulose nanofibres with lactic acid and ultrasonication (Paper I and II), and combining cellulose nanofibres with hydrophobic materials, such as polyurethane (Paper III) and lignin-rich entities (Paper IV). By using these methods, the preparation time was improved by 75% (Paper II) and by 70% (Paper IV) respectively. All reported nanopapers were significantly more tolerant of water and moisture than the reference nanopaper. The mechanical properties were also improved in Paper I and IV. Additionally, all reported nanopapers were thermally stable. This thesis also discusses the importance of quick draining in cellulose nanofibre-reinforced paper products. The results of this study are likely to aid the commercialisation of cellulose nanopapers in practical applications and the use of cellulose nanofibres in other materials, such as reinforcing paperboards. All methods used in this thesis are water-based. / Tiivistelmä Selluloosapohjaiset nanopaperit ovat lujimpia tunnettuja polymeerimateriaaleja ja lähitulevaisuudessa niiden voidaan odottaa luovan perustan useille funktionaalisille materiaaleille. Nanopaperit ovat saaneet paljon huomiota ympäristöystävällisyytensä, uusiutuvan raaka-aineensa ja biohajoavuutensa ansiosta. Lisäksi niiden valmistusprosessi on vesipohjainen ja samankaltainen kuin tavallisen paperin valmistukseen käytetty teollinen prosessi. Käyttöominaisuuksiltaan ne ovat erinomaisia, sillä vaikka niiden sitkeys on parempi kuin tunnetuilla muoveilla, ovat ne silti paperin tavoin taiteltavia. Kiehtovista ominaisuuksistaan huolimatta selluloosapohjaiset nanopaperit ovat kuitenkin vielä kaukana kaupallistamisesta ja tähän vaikuttavat pääosin kaksi tekijää. Tärkein syy on selluloosananokuitujen kuivattamisen ja näin ollen nanopaperin muodostamisen vaatima huomattavan pitkä aika. Nykyisillä menetelmillä nanopaperin valmistaminen kestää useita tunteja. Toinen syy on niiden erittäin huono veden- ja kosteudenkestävyys. Ne menettävät jopa 90 % jäykkyydestään veden vaikutuksesta, mikä rajoittaa niiden käyttöä kosteissa ja vesiroiskeille alttiissa kohteissa. Tämän väitöskirjatutkimuksen päätavoitteena on löytää ekologisesti kestävä ja teollisuudessa hyödynnettävissä oleva menetelmä molempien edellä mainittujen ongelmien ratkaisemiseksi. Työssä noudatetaan kahta eri lähestymistapaa: lisätään selluloosananokuitujen hydrofobisuutta maitohapon ja ultrasonikoinnin avulla (Artikkelit I ja II), ja yhdistetään selluloosananokuituihin hydrofobisia materiaaleja, kuten polyuretaania (PU) (Artikkeli III) ja ligniinipitoisia yhdisteitä (Artikkeli IV). Näitä menetelmiä käyttämällä valmistusaikaa saatiin lyhennettyä 75 % (Artikkeli II) ja 70 % (Artikkeli IV). Kaikki valmistetut nanopaperit olivat huomattavasti veden- ja kosteudenkestävämpiä kuin verrokkinäytteet sekä osoittivat lämpöstabiiliutta. Lisäksi mekaanisia ominaisuuksia saatiin parannettua Artikkeleissa I ja IV. Tässä työssä käsitellään myös nopean kuivattamisen tärkeyttä selluloosananokuitulujitteisten paperituotteiden valmistuksessa. Saadut tulokset todennäköisesti edistävät selluloosapohjaisten nanopaperien kaupallistamista ja selluloosananokuitujen hyödyntämistä esimerkiksi kartongin lujitemateriaalina. Kaikki työssä käytetyt menetelmät ovat vesipohjaisia.