This dissertation aimed to assess whether tannins were able to prevent boron leaching using heat treatment. First, to understand tannin behavior under high temperatures a pilot test was performed. Tannin powder from the Quebracho tree was dissolved into deionized water (DW). Southern yellow pine (SYP) and yellow-poplar (YP) woods were impregnated with tannins under a full cell process. Heat treatment under N2 atmosphere at 190/195/210°C was evaluated for four hours for both species. Mass loss due to heat treatment for wood and tannin as well as radial and tangential shrinkage were calculated. FT-IR spectroscopy and scanning electron microscopy were performed to understand the phenomena. Results indicated that at temperatures above 190°C there was an excessive tannin mass loss with collapse formation on SYP tannin-treated samples as well as changes in the in the spectra. The detailed study used 80 g of tannins and 12 g of DOT into 800 g of DW to attempt preventing boron leaching. SYP and YP samples were impregnated through full cell process and heat treated under N2, at 190°C for four hours. Samples were leached for 15 days. Anti-swelling efficiency was calculated. The resistance of the woods was tested against Gloeophyllum trabeum and Trametes versicolor fungi as well as the subterranean termite Reticulitermes flavipes for leached and unleached samples. The mass loss due to heat treatment was higher in YP than in SYP. The color changed for both woods, turning into much darker after tannin impregnation and heat treatment. All treatments for both species had lower volumetric shrinkage when compared to control as an effect of heat treatment, leading to improvement in dimensional stability. When mixed with tannins and heat treated, DOT remained in wood with leaching reduction of 46.5% and 34.5% for SYP and YP, respectively. After 15 days leaching HT T/DOT samples were classified as resistant (SYP) and highly resistant (YP) to the attack of decay fungi. Heat treated wood had improvement in durability against R. flavipes. HT DOT leached samples had 20.6% mass loss, whereas HT T/DOT 13.8%. Future work with amine-tannin solution should be tested to improve the leaching reduction.

Biobased materials made from renewable resources, such as wood, play an important role in the sustainable development of society. One main challenge of biobased building materials is their inherent moisture sensitivity, a major cause for fungal decay, mold growth and dimensional instability, resulting in decreased service life as well as costly maintenance. A new building material known as wood-plastic composites (WPCs) has emerged. WPCs are a combination of a thermoplastic matrix and a wood component, the former is usually recycled polyethylene or polypropylene, and the latter a wood processing residual, e.g. sawdust and wood shavings. The objective of this thesis was to gain more insight about characteristics of WPCs containing a modified wood component. The hypothesis was that a modified wood component in WPCs would increase the moisture resistance and durability in outdoor applications. The study comprises both injection molded and extruded WPC samples made with an unmodified, acetylated, thermally modified or furfurylated wood component in a polypropylene (PP), high density polyethylene (HDPE), cellulose ester (CAP, a cellulose ester containing both acetate and propionate substituents) or polylactate (PLA) matrix. The WPCs were prepared with 50-70 weight-% wood. The emphasis was on studying the moisture sorption, fungal resistance and micromorphological features of these new types of composites. Water sorption in both liquid and vapor phases was studied, and the biological performance was studied both in laboratory and in long term outdoor field tests. Micromorphological features were assessed by analyzing of the wood component prior to and after processing, and by studying the composite microstructure by means of a new sample preparation technique based on UV excimer laser ablation combined with scanning electron microscopy (SEM). Results showed that the WPCs with a modified wood component had a distinctly lower hygroscopicity than the WPCs with unmodified wood, which resulted in less wood-plastic interfacial cracks when subjected to a moisture soaking-drying cycle. Durability assessments in field and marine tests showed that WPCs with PP or CAP as a matrix and 70 weight-% unmodified wood degraded severely within a few years, whereas the corresponding WPCs with a modified wood component were sound after 7 years in field tests and 6 years in marine tests. Accelerated durability tests of WPCs with PLA as a matrix showed only low mass losses due to decay. However, strength losses due to moisture sorption suggest that the compatibility between the PLA and the different wood components must be improved. The micromorphological studies showed that WPC processing distinctly reduces the size and changes the shape of the wood component. The change was most pronounced in the thermally modified wood component which became significantly reduced in size. The disintegration of the modified wood components during processing also creates a more homogeneous micromorphology of the WPCs, which may be beneficial from a mechanical performance perspective. Future studies are suggested to include analyses of the surface composition, the surface energy and the surface energy heterogeneity of both wood and polymer components in order to tailor new compatible wood-polymer combinations in WPCs and biocomposites. / <p>QC 20121119</p>

No description available.

Made available in DSpace on 2014-08-20T13:34:25Z (GMT). No. of bitstreams: 1 Dissertacao Pedro Henrique Gonzalez de Cademartori.pdf: 2886719 bytes, checksum: 352a362f9db748d742e87be22ddaa1b0 (MD5) Previous issue date: 2012-12-17 / This study aimed to evaluate physicomechanical and chemical behaviour of Eucalyptus grandis, Eucalyptus saligna e Eucalyptus cloeziana thermally modified wood. To achieve this, six trees of each species were randomly selected and samples measuring 1.6 x 1.6 x 25cm were prepared. The samples were thermally modified through exposure to nine treatments in an oven and in an autoclave steriliser. The process conditions in the oven were: temperatures between 180 and 240ºC and time of exposure of 4h, whereas for the treatments in autoclave a constant temperature (127°C) and pressure (1.5kgf/cm²) were used for 1h. The evaluation of the physical properties was done through the performance of weight loss, equilibrium moisture content, stability dimensional and specific gravity tests. Colour changes and wettability were measured by colorimetric and contact angle techniques, respectively. Regarding mechanical properties, thermally modified wood was evaluated through the performance of static bending tests and non-destructive ultrasonic tests. Chemical modifications were qualitatively measured through infrared spectroscopy (ATR-IR). The main results showed that thermal treatments significantly influenced weight loss, equilibrium moisture content and dimensional stability. On the other hand, specific gravity did not show a great behaviour in order to explain the influence of thermal treatments on wood. A gradual darkening in both radial and tangential sections was observed, mainly due to a high reduction of L* after treatment 2 (180°C), since a* and b* showed distinct behaviour. Generally, stiffness remained constant when related to the control treatment, whereas mechanical strength decreased significantly, mainly after the treatments 6, 7, 8 and 9. The use of the non-destructive ultrasound technique obtained coefficients of determination between 0.66 and 0.80 for the relationship MOE x Ed. The wettability of thermally modified wood presented the best results in the treatments 2, 3, 4 and 5 for all the species, with the contact angle increasing and remaining with high stability as a function of time of exposure. Infrared spectroscopy showed modifications in different peaks, mainly related to the hemicelluloses and crystallinity of the structure, representing thermal degradation of the material as a function of temperature of treatment. Therefore, the thermal treatments reduced hygroscopicity and modified the colour of the wood. The mechanical strength was reduced significantly and the ultrasound was efficient in order to estimate the modulus of elasticity. Wettability decreased significantly as a function of the thermal treatments and infrared spectroscopy (ATR-IR) demonstrated to be an excellent tool for the qualitative analysis of chemical modifications due to thermal treatments. / O presente estudo objetivou avaliar o comportamento físico, mecânico e químico das madeiras de Eucalyptus grandis, Eucalyptus saligna e Eucalyptus cloeziana submetidas a diferentes tratamentos de termorretificação. Para tal, selecionaram-se ao acaso seis árvores de cada espécie para a confecção de corpos de prova com dimensões de 1,6 x 1,6 x 25cm. Submeteram-se os corpos de prova a nove tratamentos de termorretificação a partir da utilização de uma estufa e uma autoclave de esterilização. As condições de processo para os tratamentos em estufa foram temperatura entre 180 e 240°C e tempo de exposição de 4h, enquanto que a temperatura dos tratamentos em autoclave permaneceu constante em 127°C e pressão de 1,5 kgf/cm² durante 1h. A avaliação das propriedades físicas foi realizada por meio de ensaios de perda de massa, teor de umidade de equilíbrio, estabilidade dimensional e massa específica. Verificaram-se as alterações na coloração e molhabilidade por meio das técnicas de colorimetria e ângulo de contato, respectivamente. Mecanicamente, o material foi avaliado por meio de ensaios de flexão estática e ultrassom. As modificações químicas foram avaliadas qualitativamente por espectroscopia no infravermelho (ATR-IR). Os principais resultados mostraram significativa influência da termorretificação na perda de massa, teor de umidade de equilíbrio e estabilidade dimensional. Por outro lado, a massa específica não apresentou comportamento capaz de explicar a influência da termorretificação. Observou-se escurecimento gradual na madeira das três espécies em ambas as seções, em que se ressalta uma forte redução do L* após o tratamento 2 (180°C), diferentemente do a* e b* que apresentaram comportamento distinto. Verificou-se que, enquanto a rigidez da madeira termorretificada manteve-se inalterada quando relacionada ao tratamento de referência, a resistência do material foi significativamente reduzida, principalmente após os tratamentos 6, 7, 8 e 9. Já a utilização da técnica não destrutiva de ultrassom permitiu a obtenção de coeficientes de determinação entre 0,66 e 0,80 para a relação MOE x Ed. A molhabilidade da madeira termorretificada apresentou os melhores resultados para os tratamentos 2, 3, 4 e 5 na madeira das três espécies, em que o ângulo de contato elevou-se e manteve-se com maior estabilidade ao longo do tempo. A técnica de ATR-IR identificou modificações nos picos relacionados, principalmente as hemiceluloses e também à cristalinidade da estrutura, incitando a degradação térmica do material conforme o aumento da temperatura. Dessa maneira, concluiu-se que os tratamentos empregados foram suficientes para reduzir a higroscopicidade, bem como modificar os tons de cor para cada temperatura utilizada. A resistência mecânica foi significativamente reduzida e, ao mesmo tempo, o ultrassom mostrou-se eficiente quanto à predição do módulo de elasticidade. A molhabilidade da madeira reduziu significativamente conforme o emprego dos tratamentos. A ATR-IR mostrou-se como uma excelente ferramenta de análise qualitativa das modificações químicas ocorridas durante a termorretificação.

Submitted by Fred Willians Calonego null (fwcalonego@ig.com.br) on 2017-12-20T15:47:02Z No. of bitstreams: 1 Calonego FW_Doutorado 2017.pdf: 5105344 bytes, checksum: b332f3457105ae9be3d54a958181484a (MD5) / Approved for entry into archive by Maria Lucia Martins Frederico null (mlucia@fca.unesp.br) on 2017-12-20T16:13:09Z (GMT) No. of bitstreams: 1 calonego_fw_dr_bot.pdf: 5105344 bytes, checksum: b332f3457105ae9be3d54a958181484a (MD5) / Made available in DSpace on 2017-12-20T16:13:09Z (GMT). No. of bitstreams: 1 calonego_fw_dr_bot.pdf: 5105344 bytes, checksum: b332f3457105ae9be3d54a958181484a (MD5) Previous issue date: 2017-11-13 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / No Brasil, a espécie pioneira Schizolobium parahyba (Vell.) Blake, conhecida como Guapuruvu, tem potencial para os projetos de restauração ecológica da Floresta Atlântica, e quando atingem cerca de 15 anos podem ser retiradas mediante plano de manejo. Entretanto, uma característica indesejável da sua madeira é a presença acentuada de lenho juvenil e uma das suas limitações é a baixa durabilidade natural. Uma forma de minimizar este problema é a modificação térmica logo após a sua secagem. Porém, esses tratamentos provocam mudanças na cor da madeira. Assim, o objetivo desse estudo foi avaliar o efeito do tratamento de modificação térmica nas propriedades físicas, químicas e colorimétricas e na resistência dos lenhos juvenil e adulto de S. parahyba aos organismos xilófagos e ao intemperismo. Para tanto, foram usadas tábuas provenientes de toras de Guapuruvu, com cerca de 15 anos de idade, retiradas de uma área de recuperação florestal da Faculdade de Ciências Agronômicas, da UNESP, de Botucatu-SP. Cada tábua foi seccionada de modo a fornecer peças controle e outras destinadas para os tratamentos de modificação térmica, com temperaturas finais de 180ºC, 200ºC e 220ºC. Corpos de prova foram retirados para a caracterização tecnológica dos lenhos juvenil e adulto através dos ensaios de propriedades físicas, químicas, de caracterização colorimétrica da madeira e de resistências aos fungos de podridão parda Gloeophyllum trabeum e de podridão branca Pycnoporus sanguineus, ao cupim de madeira seca Cryptotermes brevis e ao intemperismo. Os resultados mostraram que: (1) o aumento da temperatura de modificação térmica promove decréscimos significativos de até 9,1% na massa específica aparente a 21ºC e 65% de umidade relativa da madeira de S. parahyba, e reduz em até 51,1% e 54,1% os seus respectivos teores de umidade de equilíbrio e inchamento volumétrico; (2) a massa específica básica e os coeficientes de retratibilidades não variam com os tratamentos térmicos e não são indicados para avaliar a qualidade da madeira modificada termicamente; (3) a modificação térmica provoca reduções significativas de até 25,0% nos teores de holocelulose e um aumento proporcional de até 41,7% e 286,5% nos respectivos teores de lignina e de extrativos totais da madeira; (4) a cor da madeira sem tratamento é classificada como branco amarelada, pois apresenta alta claridade (L* de 80,41 a 80,85) e presença marcante do pigmento amarelo (b* de 19,06 a 20,07), e o tratamento térmico provoca o seu escurecimento e avermelhamento; (5) a madeira sem tratamento é classificada como não resistente ao cupim de madeira seca e ao fungo de podridão parda, e, de resistência moderada ao fungo de podridão branca, sendo que os tratamentos térmicos provocam reduções significativas de até 90,6% nas perdas de massa provocadas pelos fungos apodrecedores e não mudam a classe de resistência da madeira aos cupins; e (6) a madeira sem tratamento ficou mais escurecida, avermelhada e amarelada após o intemperismo, e o tratamento térmico aumenta a sua resistência aos agentes abióticos. Pode-se concluir que a modificação térmica possui um grande potencial para melhorar a estabilidade dimensional e a resistência natural da madeira de S. parahyba aos fungos apodrecedores e ao intemperismo, embora, modifique a sua cor e não altera a sua classe de resistência aos cupins. / In Brazil, the pioneer plant species Schizolobium parahyba (Vell.) Blake, known as Guapuruvu, has potential for ecological restoration projects in the Atlantic Forest, and when they reach about 15 years can be taken by the management plan. However, an undesirable feature of this wood is the pronunced presence of juvenile wood and a limitation is low biological resistance. An attractive way to mitigate this problem is this thermal modification process after its drying. However, these thermal treatments cause changes in color of wood. The aim of this study was to evaluate the effect of thermal modification on physicochemical and colorimetric properties and biological resistance of juvenile and mature woods from S. parahyba to xylophagous organisms and weathering. Boards were taken from a 15-year-old S. parahyba forest recovery area of Agronomy Sciences College from UNESP, located in Botucatu, SP, Brazil. Each board was sawed into smaller pieces measuring 0.60 m in length. One small piece was kept in its original condition (untreated wood), whereas the other pieces were reserved for the thermal treatments at final temperature of 180ºC, 200ºC, and 220ºC. Subsequently, samples were cut from all the boards (untreated and thermally modified woods) to technological characterization for both juvenile and mature wood across to tests of physical and chemical properties, colorimetric characterization of wood, decay resistance at brown-rot fungus Gloeophyllum trabeum and white-rot fungus Pycnoporus sanguineus, biological resistance to térmite dry wood Cryptotermes brevis, and weathering resistance. The results showed that: (1) the increase in the thermal modification temperature causes significant decreases of up to 9,1% in the density at 21ºC and 65% relative humidity of the S. parahyba wood and reduces the equilibrium moisture content and volumetric swellings in up to 51.1% and 54.1%, respectively; (2) the density basic and dimensional change coefficient of wood were not the most suitable for evaluating the quality of thermally modified wood; (3) the thermal modification causes significant decreases of up to 25.0% in the holocelulloses contents, an proportional increase of up to 41.7% e 286.5% in the lignin and extractives contents, respectively; (4) the color of untreated wood can be classified by yellowish white, because presents high brightness (L* of 80.41 to 80.85) and strong presence of yellow pigment (b* of 19.06 to 20.07), and the thermal treatment causes the darkening and reddening of timber; (5) the untreated wood was classified as non-durable to the dry wood termites and brown-rot fungus, and also was classified as moderate resistance to the white-rot fungus, whereas the thermal modification promotes significant reductions of up to 90.6% in the weight losses caused by rot fungi and do not change the damage caused by termites in wood; and (6) the untreated wood showed darkening, a reddish behavior and a yellowish behavior after weathering tests, and the thermal modification causes significant decreases in the weathering of wood. We concluded that the thermal modification has a great potential to improve the dimensional stability and the natural resistance of S. parahyba wood to decay fungi and weathering, although it modifies the color of wood and does not change its resistance class to the termite.

Ein Teil der Arbeit beschäftigt sich mit der Aufarbeitung zur anatomischen und chemischen strukturellen Zusammensetzung von vorrangig einheimischen Hölzern, um schließlich die physikalischen Eigenschaften bzw. deren Differenzen, auch im Unterschied zwischen Laub- und Nadelholz phänomenologisch im Sinne der Struktur-Eigenschafts-Beziehungen zu verstehen. Die Verbesserung von holzphysikalischen Defiziten wird im Rahmen der Arbeit hauptsächlich mithilfe von physikalischen Verfahren erläutert. Dazu erfolgen ausführliche Beschreibungen zum mechanischen Verdichten quer zur Faserrichtung des Holzes, der thermischen Modifikation sowie der Kombination aus beiden Verfahren. Dazu werden sowohl jeweils die verfahrenstechnischen Parameter und Vorgehensweisen als auch die resultierenden anatomischen, chemischen und den damit verbundenen physikalischen Eigenschaftsänderungen erläutert, insbesondere in Abhängigkeit der Parameteranwendung sowie im Unterschied zwischen Laub- und Nadelholz. Des Weiteren widmet sich die Arbeit mit bereits stattgefundenen Untersuchungen zur physikalischen, chemischen und biologischen Holzmodifikation zur Verbesserung von akustischen Eigenschaftenvon Hölzern und deren mögliche Eignung im Musikinstrumentenbau zusammengefasst und jeweils bewerten. Schließlich werden zwei ausgewählte Fallbeispiele beschrieben, welche die Zielsetzung verfolgten, einheimische Holzarten mithilfe der physikalischen Holzmodifikation als Tropenholzersatz in Konzertgitarren und Elektro-Bassgitarren bauteilspezifisch zu verwenden. Der jeweilige Lösungsansatz wurde einerseits durch Einsatz der thermischen Modifikation und andererseits mithilfe einer Kombination aus dem Plastifizieren, mechanischen Verdichten quer zur Faserrichtung und der anschließenden thermischen Modifikation verfolgt. Zur Material- und Instrumentencharakterisierung wurden hierbei verschiedene Testmethoden verwendet und bewertet.:1 Einleitung 1 1.1 Hintergrund und Motivation 1 1.2 Aufbau und Vorgehensweise 5 2 Struktureller Aufbau und relevante Eigenschaften von Holz 6 2.1 Anatomie des Holzes 6 2.2 Chemie des Holzes 18 2.3 Physik des Holzes 39 3 Holzmodifikation 91 3.1 Allgemeines 91 3.2 Verdichten quer zur Faserrichtung 95 3.3 Thermische Modifikation 119 3.4 Kombination: Querverdichten und thermische Behandlung 167 4 Holzmodifikation im Musikinstrumentenbau 185 5 Thermische Modifikation am Beispiel von Klassikgitarren 221 5.1 Grundlagen und Erwartungen 221 5.2 Technologische Umsetzung 230 5.3 Prüfmethoden und Bewertungskriterien 233 5.4 Ergebnisse und Diskussion 247 5.4.1 Allgemeines 247 5.4.2 Optik, Rohdichte und Sorption 248 5.4.3 Mechanische Kennwerte 254 5.4.4 Akustische Kennwerte 262 5.4.5 Objektives Klangverhalten (Anzupftests) 271 5.4.6 Subjektives Klangverhalten (Spieltests) 276 6 Kombination von Querverdichten und thermische Behandlung am Beispiel des Griffbrettbaus für Elektro-Bassgitarren 285 6.1 Grundlagen und Erwartungen 285 6.2 Technologische Umsetzung 291 6.3 Prüfmethoden und Bewertungskriterien 294 6.4 Ergebnisse und Diskussion 296 6.4.1 Allgemeines 296 6.4.2 Optik, Rohdichte, Sorption 298 6.4.3 Mechanische Kennwerte 312 6.4.4 Akustische Kennwerte 315 6.4.5 Objektives Klangverhalten (Anzupftests) 323 6.4.6 Subjektives Klangverhalten (Spieltests) 327 7 Zusammenfassung 330 8 Ausblick 338 Literaturverzeichnis 340 Abbildungsverzeichnis 379 Tabellenverzeichnis 394 / One part of the thesis deals with the processing of the anatomical and chemical structural composition of primarily native woods in order to finally understand the physical properties and their differences, also in the difference between hardwood and softwood phenomenologically in the sense of structure-property relationships. The improvement of wood-physical deficits is mainly explained within the scope of the work with the help of physical methods. Detailed descriptions are given of mechanical densification across the grain direction of the wood, thermal modification and the combination of both methods. The process parameters and procedures as well as the resulting anatomical, chemical and associated physical property changes are explained, in particular depending on the parameter application and the difference between hardwood and softwood. Furthermore, the work is dedicated to studies that have already taken place on physical, chemical and biological wood modification to improve the acoustic properties of woods and their possible suitability in musical instrument making, summarized and evaluated in each case. Finally, two selected case studies are described which pursued the objective of using native wood species as a component-specific substitute for tropical wood in concert guitars and electric bass guitars with the aid of physical wood modification. The respective solution approach was pursued on the one hand by using thermal modification and on the other hand by using a combination of plasticizing, mechanical densification across the grain direction and subsequent thermal modification. Various test methods were used and evaluated for both material and instrument characterization.:1 Einleitung 1 1.1 Hintergrund und Motivation 1 1.2 Aufbau und Vorgehensweise 5 2 Struktureller Aufbau und relevante Eigenschaften von Holz 6 2.1 Anatomie des Holzes 6 2.2 Chemie des Holzes 18 2.3 Physik des Holzes 39 3 Holzmodifikation 91 3.1 Allgemeines 91 3.2 Verdichten quer zur Faserrichtung 95 3.3 Thermische Modifikation 119 3.4 Kombination: Querverdichten und thermische Behandlung 167 4 Holzmodifikation im Musikinstrumentenbau 185 5 Thermische Modifikation am Beispiel von Klassikgitarren 221 5.1 Grundlagen und Erwartungen 221 5.2 Technologische Umsetzung 230 5.3 Prüfmethoden und Bewertungskriterien 233 5.4 Ergebnisse und Diskussion 247 5.4.1 Allgemeines 247 5.4.2 Optik, Rohdichte und Sorption 248 5.4.3 Mechanische Kennwerte 254 5.4.4 Akustische Kennwerte 262 5.4.5 Objektives Klangverhalten (Anzupftests) 271 5.4.6 Subjektives Klangverhalten (Spieltests) 276 6 Kombination von Querverdichten und thermische Behandlung am Beispiel des Griffbrettbaus für Elektro-Bassgitarren 285 6.1 Grundlagen und Erwartungen 285 6.2 Technologische Umsetzung 291 6.3 Prüfmethoden und Bewertungskriterien 294 6.4 Ergebnisse und Diskussion 296 6.4.1 Allgemeines 296 6.4.2 Optik, Rohdichte, Sorption 298 6.4.3 Mechanische Kennwerte 312 6.4.4 Akustische Kennwerte 315 6.4.5 Objektives Klangverhalten (Anzupftests) 323 6.4.6 Subjektives Klangverhalten (Spieltests) 327 7 Zusammenfassung 330 8 Ausblick 338 Literaturverzeichnis 340 Abbildungsverzeichnis 379 Tabellenverzeichnis 394

The solvent-induced swelling behaviour of Victorian brown coals was examined in detail to probe the bonding mechanisms in very low rank coals (in this case Victorian brown coal). Correlation of solvent properties with differences in observed swelling behaviour were interpreted in terms of the coal structure, and means of predicting the observed behaviour were considered. Modification of the coal structure via physical compression (briquetting), chemical digestion, thermal modification, and functional group alkylation was used to further elucidate those structural features which govern the swelling behaviour of Victorian brown coals. Briquette weathering (i.e. swelling and disintegration of briquettes when exposed to variations in humidity and temperature) was examined by making alterations to briquette feed material and observing the effects on swelling in water. The application of solubility parameter alone to prediction of coal swelling was rejected due to the many exceptions to any proposed trend. Brown coal swelling showed a minimum when the solvent electron-donor number (DN) minus its electron-acceptor number (AN) was closest to zero, i.e. when DN and AN were of similar magnitude. The degree of swelling increased either side of this point, as predicted by theory. In contrast to the solubility parameter approach (which suffers from the uncertainty caused by specific interaction between coal and solvent), the electron donor/acceptor approach is about specific interactions. It was concluded that a combination of total and three-dimensional solubility parameters and solvent electron donor/acceptor numbers may be used to predict solvent swelling of unextracted brown coals with some success. Solvent access to chemically densified coal was found to be insensitive to a reduction in pore volume, and chemical effects were dominant. Thermal modification of the digested coal resulted in reduced swelling for all solvents, indicating that the structure had adopted a minimum energy configuration due to decarboxylation and replacement of hydrogen bonds with additional covalent bonds. Swelling of oxygen-alkylated coals demonstrated that the more polar solvents are able to break relatively weak hydrogen bonded crosslinks. The large difference between the rate and extent of swelling in water (and hence weathering) of Yallourn and Morwell briquettes was shown to be almost entirely attributable to exchanged magnesium. Magnesium exchange significantly increases the rate and extent of swelling of Yallourn coal. It was also shown that the swelling of briquettes due to uptake of water by magnesium-exchanged coals is reduced significantly with controlled ageing of the briquettes. The solvent swelling behaviour of Victorian brown coals is consistent with the notion that coal is a both covalently and non-covalently crosslinked and entangled macromolecular network comprising extractable species, which are held within the network by a wide range of non-covalent, polar, electron donor/acceptor interactions. Solvents capable of significant extraction of whole brown coals are also capable of significant swelling, but not dissolution, of the macromolecular coal network, which supports the view that the network is comprised of both covalent and ionic bonding. Victorian brown coals have also been shown to exhibit polyelectrolytic behaviour due to a high concentration of ionisable surface functionalities.

Abstract Wood is an essential material that has many applications in the fields of engineering and especially in the forest industry, which is particularly important in Fennoscandia. Among the various modification methods for wood, thermal modification has grown substantially over the past decades. It is an environmentally friendly method for increasing the lifetime and usability of timber. The aim of this thesis is to characterize the properties of thermally modified wood as well as to obtain new information on the changes taking place in pinewood due to the thermal modification process. Several NMR methods were used to gain information on the effect of thermal modification on the microstructure and moisture components of Pinus sylvestris pinewood. Pinewood samples thermally modified at different temperatures were studied and compared to corresponding unmodified wood samples. Diffusion of water and methane was studied using pulsed-field-gradient stimulated-echo measurements to determine the highly anisotropic size distribution of pores in different cell structures of pinewood. NMR cryoporometry and relaxometry measurements were conducted to gain information on the amounts and environments of both the bound and free water absorbed into the wood samples. Cryoporometry measurements resulted in an upper limit value for the size of bound water sites and the combination of cryoporometry and relaxometry data enabled the size determination of cell wall micropores. Magnetic resonance imaging was used to visualize the spatial distribution of absorbed free water in the studied samples. Together these methods give a broad overall picture of the effects of the modification process. The results of this work give new insight into the microstructure of thermally modified pinewood and its relationship to moisture, which is of importance for both wood science as well as industry. The applicability of the NMR techniques used here to the study of wood is also proven in this work. Using the techniques developed, it is possible to determine the optimal modification temperature, which is high enough to obtain the desired effects, but low enough not to destroy the microstructure of wood. / Tiivistelmä Puuta pystytään hyödyntämään useilla eri aloilla ja se on materiaalina tärkeä etenkin Fennoskandiassa merkittävälle metsäteollisuudelle. Useiden erilaisten puun käsittelymenetelmien joukossa lämpökäsittely on kasvattanut voimakkaasti suosiotaan viime vuosikymmeninä. Kyseessä on ympäristöystävällinen menetelmä, jolla voidaan pidentää puun käyttöikää sekä käytettävyyttä erilaisissa sovelluskohteissa. Tämän väitöskirjan päämääränä on ollut lämpökäsitellyn puun ominaisuuksien tutkiminen ja uuden tiedon saaminen puussa lämpökäsittelyprosessin myötä tapahtuvista muutoksista. Työssä käytettiin useita eri NMR-menetelmiä lämpökäsitellyn mäntypuun (Pinus sylvestris) mikrorakenteen sekä puussa olevan kosteuden aiheuttamien vaikutusten tutkimiseksi. Työssä tutkittiin eri lämpötiloissa käsiteltyjä mäntypuunäytteitä, joita verrattiin vastaaviin käsittelemättömiin näytteisiin. Veden ja metaanin diffuusiota tutkittiin PGSTE-menetelmällä puun erittäin anisotrooppisen solurakenteen sisältämien huokosten mittojen määrittämiseksi. NMR-kryoporometria- ja -relaksometriamittaukset antoivat tietoa puuhun imeytyneen sidotun ja vapaan veden määrästä ja esiintymisympäristöstä. Kryoporometria-mittausten tuloksista saatiin yläraja sidotun veden esiintymispaikkojen koolle, ja kryoporometria- ja relaksometriamittausten tuottaman tiedon yhdistäminen mahdollisti soluseinämien mikrohuokosten koon määrittämisen. Magneettikuvausta käytettiin näytteisiin absorboituneen veden avaruudellisen jakauman määrittämiseen. Käytetyt menetelmät tarjoavat laajan kokonaiskuvan lämpökäsittelyprosessin vaikutuksista puulle. Tämän työn tulokset antavat puutiedettä ja -teollisuutta hyödyttävää uutta tietoa lämpökäsitellyn männyn mikrorakenteesta sekä sen suhteesta kosteuteen. Väitöskirja myös osoittaa käytettyjen NMR-menetelmien soveltuvan hyvin puun tutkimiseen. Tämän tutkimuksen myötä kehitettyjen menetelmien avulla voidaan määrittää mm. optimaalinen lämpökäsittelylämpötila, joka on riittävän korkea haluttujen ominaisuuksien kannalta aiheuttamatta kuitenkaan puun mikrorakenteen hajoamista.

’African Bamboo PLC’ has the vision to become the first and the leading bamboo-based floorboard producer in Africa with export markets in Europe and America. African alpine bamboo (Yushania alpina), common in the highlands of Ethiopia, was used to develop woven strand board (WSB) products. Research on thermal modification was part of the product development. Samples were mainly collected in Tetechia (6°33‘ 34‘‘ N 38°32‘25‘‘ W, 2,650-2,700 m a.s.l.), located in the Sidama region. Three culms each of two, three, four and five years of age were harvested. Samples were taken from the middle of each internode to determine the moisture content and density. Samples used to assess the effects of thermal modification were cut next to them. Further test specimens from different areas and other species such as the lowland bamboo (Oxytenanthera abyssinica) were also investigated. The thermal treatment was applied in a kiln with steam as an inert blanket to reduce oxidative processes. Eight modifications were performed at temperatures of 160 °C, 180 °C, 200 °C and 220 °C, at durations of three or five hours each. Mass loss, sorption behaviour, impact resistance, resistance to indentation and contents of chemical components were analysed for the modified and unmodified samples. Yushania alpina is a thin-walled bamboo with a maximum diameter of 6 cm, moisture content of up to 150 % and densities of between 0.5 g/cm² and 0.8 g/cm². Moisture content, diameter and wall thickness decreased from the bottom to the top of the culms, whereas density increased. Two year old bamboo had the lowest and three year the highest density. The mass loss followed an exponential trend, with about 2 % loss at 160 °C and 16 % at 220 °C. This mainly reflected the degradation of hemicellulose, which was fully removed at 220 °C. Extractive contents, at less than 5 %, fluctuated. Lignin amounted to 30 % and increased appreciably. Cellulose reached contents of about 45 % and decreased slightly at high temperatures. The chemical change, which was based more on the temperature than on the duration of treatment, influenced the sorption behaviour and mechanical properties most of all. The equilibrium moisture content was reduced by between 10 % to 40 %, depending on the climate and modification temperature chosen. This reduction stabilised between temperatures of 200 °C and 220 °C. The impact resistance of untreated bamboo was 3.8 J/cm², compared to only 1.4 J/cm² for modified samples. Resistance also differed between samples from the outer and inner part of the culm in the transverse section. The resistance to indentation declined also. Unmodified samples had 47 N/mm², compared to only 20 N/mm² for strongly modified samples. The results of the analysis and the experience gained indicate that temperatures between 180 °C and 200 °C, held for three hours, lead to the best results for woven strand board production using Ethiopian highland bamboo. / ’African Bamboo PLC’ setzt sich zum Ziel, als erstes Unternehmen Holzwerkstoffe aus Bambus nach Europa und Amerika zu exportieren. Afrikanischer Hochgebirgsbambus (Yushania alpina), welcher vor allem im Hochland von Äthiopien vorkommt, wurde dazu verwendet ”woven strand boards” (WSB) zu entwickeln. Untersuchungen zur thermischen Modifizierung waren dabei Bestandteil der Produktentwicklung. Die dafür notwendigen Bambusproben wurden hauptsächlich in Tetechia (6°33‘34‘‘ N 38°32‘25‘‘ W, 2650-2700 m ü. NN), einem Dorf in Sidama, entnommen. Es wurden dazu je drei Bambushalme der Altersklassen zwei, drei, vier und fünf Jahre geerntet. Proben für die Bestimmung von Holzfeuchte und Dichte wurden in der Mitte jedes Internodiums entnommen. Diese spielten als Referenzprobe eine große Rolle. Neben den Referenzprobekörpern wurden die jeweiligen Stücke für die thermische Behandlung heraus gesägt, wobei dies nach einer bestimmten Systematik erfolgte. Neben den Proben aus Tetechia wurden für die Untersuchungen zudem Proben aus anderen Gebieten und von einer anderen Art, dem Tieflandbambus (Oxytenanthera abyssinica), hinzugefügt. Die thermische Modifizierung erfolgte unter Wasserdampf, welcher oxidative Prozesse verhinderte. Insgesamt erfolgten acht Modifizierungen bei Temperaturen von 160 °C, 180 °C, 200 °C und 220 °C und einer jeweiligen Haltezeit von drei oder fünf Stunden. In Anbetracht der unbehandelten und behandelten Proben wurden der Masseverlust, die Bruchschlagarbeit, der Eindruckswiderstand und die chemische Zusammensetzung analysiert. Yushania alpina ist ein dünnwandiger Bambus mit Durchmessern bis zu 6 cm, Holzfeuchten bis 150 % und Dichten zwischen 0,5 g/cm² und 0,8 g/cm². Holzfeuchte, Durchmesser und Wandstärke verringerten sich mit der Halmhöhe, wobei die Dichte hingegen anstieg. Zweijähriger Bambus hatte die geringsten und dreijähriger Bambus die höchsten Dichten. Der Masseverlust folgte einem expontiellem Verlauf mit Werten von 2 % bei 160 °C und 16 % bei 220 °C. Er widerspiegelte den Abbau der Hemicellulose, welche bei 220 °C schon nicht mehr vorhanden war. Exktraktgehalte fluktuierten mit Werten unter 5 %. Der Ligningehalt lag bei ungefähr 30 % und stieg merklich an. Der Cellulosegehalt erreichte Werte von etwa 45 %, wobei die Cellulose bei höheren Temperaturen leicht abgebaut wurde. Die chemischen Veränderungen, welche maßgeblich von der angewandten Temperatur statt der Behandlungsdauer beeinflusst wurden, wirkten sich auf das Sorptionsverhalten und mechanische Eigenschaften aus. Je nach ausgesetztem Klima und erfolgter Modifikation wurde die Ausgleichsfeuchte der Proben um 10 % bis 40 % reduziert. Die Abnahme der Ausgleichsfeuchte stabilisierte sich im Temperaturbereich von 200 °C bis 220 °C. Die Bruchschlagarbeit des unbehandelten Bambus betrug 3,8 J/cm², die des behandelten nur 1,4 J/cm². Die Bruchschlagarbeit variierte unabhängig von der Modifikation zwischen dem inneren und äußeren Abschnittes innerhalb des Halmquerschnitts. Der Eindruckswiderstand nahm mit der thermischen Behandlung ebenfalls ab. Unbehandelte Proben hatten 47 N/mm², während die modifizierten Proben nur noch 20 N/mm² aufwiesen. Anhand der Ergebnisse und erworbenen Erfahrungen lies sich schlussfolgern, dass Temperaturen zwischen 180 °C und 200 °C bei einer Haltezeit von drei Stunden für die thermische Modifizierung von Äthiopischem Hochlandbambus in Bezug auf die Entwicklung von ”woven strand boards” empfehlenswert waren.

’African Bamboo PLC’ has the vision to become the first and the leading bamboo-based floorboard producer in Africa with export markets in Europe and America. African alpine bamboo (Yushania alpina), common in the highlands of Ethiopia, was used to develop woven strand board (WSB) products. Research on thermal modification was part of the product development. Samples were mainly collected in Tetechia (6°33‘ 34‘‘ N 38°32‘25‘‘ W, 2,650-2,700 m a.s.l.), located in the Sidama region. Three culms each of two, three, four and five years of age were harvested. Samples were taken from the middle of each internode to determine the moisture content and density. Samples used to assess the effects of thermal modification were cut next to them. Further test specimens from different areas and other species such as the lowland bamboo (Oxytenanthera abyssinica) were also investigated. The thermal treatment was applied in a kiln with steam as an inert blanket to reduce oxidative processes. Eight modifications were performed at temperatures of 160 °C, 180 °C, 200 °C and 220 °C, at durations of three or five hours each. Mass loss, sorption behaviour, impact resistance, resistance to indentation and contents of chemical components were analysed for the modified and unmodified samples. Yushania alpina is a thin-walled bamboo with a maximum diameter of 6 cm, moisture content of up to 150 % and densities of between 0.5 g/cm² and 0.8 g/cm². Moisture content, diameter and wall thickness decreased from the bottom to the top of the culms, whereas density increased. Two year old bamboo had the lowest and three year the highest density. The mass loss followed an exponential trend, with about 2 % loss at 160 °C and 16 % at 220 °C. This mainly reflected the degradation of hemicellulose, which was fully removed at 220 °C. Extractive contents, at less than 5 %, fluctuated. Lignin amounted to 30 % and increased appreciably. Cellulose reached contents of about 45 % and decreased slightly at high temperatures. The chemical change, which was based more on the temperature than on the duration of treatment, influenced the sorption behaviour and mechanical properties most of all. The equilibrium moisture content was reduced by between 10 % to 40 %, depending on the climate and modification temperature chosen. This reduction stabilised between temperatures of 200 °C and 220 °C. The impact resistance of untreated bamboo was 3.8 J/cm², compared to only 1.4 J/cm² for modified samples. Resistance also differed between samples from the outer and inner part of the culm in the transverse section. The resistance to indentation declined also. Unmodified samples had 47 N/mm², compared to only 20 N/mm² for strongly modified samples. The results of the analysis and the experience gained indicate that temperatures between 180 °C and 200 °C, held for three hours, lead to the best results for woven strand board production using Ethiopian highland bamboo. / ’African Bamboo PLC’ setzt sich zum Ziel, als erstes Unternehmen Holzwerkstoffe aus Bambus nach Europa und Amerika zu exportieren. Afrikanischer Hochgebirgsbambus (Yushania alpina), welcher vor allem im Hochland von Äthiopien vorkommt, wurde dazu verwendet ”woven strand boards” (WSB) zu entwickeln. Untersuchungen zur thermischen Modifizierung waren dabei Bestandteil der Produktentwicklung. Die dafür notwendigen Bambusproben wurden hauptsächlich in Tetechia (6°33‘34‘‘ N 38°32‘25‘‘ W, 2650-2700 m ü. NN), einem Dorf in Sidama, entnommen. Es wurden dazu je drei Bambushalme der Altersklassen zwei, drei, vier und fünf Jahre geerntet. Proben für die Bestimmung von Holzfeuchte und Dichte wurden in der Mitte jedes Internodiums entnommen. Diese spielten als Referenzprobe eine große Rolle. Neben den Referenzprobekörpern wurden die jeweiligen Stücke für die thermische Behandlung heraus gesägt, wobei dies nach einer bestimmten Systematik erfolgte. Neben den Proben aus Tetechia wurden für die Untersuchungen zudem Proben aus anderen Gebieten und von einer anderen Art, dem Tieflandbambus (Oxytenanthera abyssinica), hinzugefügt. Die thermische Modifizierung erfolgte unter Wasserdampf, welcher oxidative Prozesse verhinderte. Insgesamt erfolgten acht Modifizierungen bei Temperaturen von 160 °C, 180 °C, 200 °C und 220 °C und einer jeweiligen Haltezeit von drei oder fünf Stunden. In Anbetracht der unbehandelten und behandelten Proben wurden der Masseverlust, die Bruchschlagarbeit, der Eindruckswiderstand und die chemische Zusammensetzung analysiert. Yushania alpina ist ein dünnwandiger Bambus mit Durchmessern bis zu 6 cm, Holzfeuchten bis 150 % und Dichten zwischen 0,5 g/cm² und 0,8 g/cm². Holzfeuchte, Durchmesser und Wandstärke verringerten sich mit der Halmhöhe, wobei die Dichte hingegen anstieg. Zweijähriger Bambus hatte die geringsten und dreijähriger Bambus die höchsten Dichten. Der Masseverlust folgte einem expontiellem Verlauf mit Werten von 2 % bei 160 °C und 16 % bei 220 °C. Er widerspiegelte den Abbau der Hemicellulose, welche bei 220 °C schon nicht mehr vorhanden war. Exktraktgehalte fluktuierten mit Werten unter 5 %. Der Ligningehalt lag bei ungefähr 30 % und stieg merklich an. Der Cellulosegehalt erreichte Werte von etwa 45 %, wobei die Cellulose bei höheren Temperaturen leicht abgebaut wurde. Die chemischen Veränderungen, welche maßgeblich von der angewandten Temperatur statt der Behandlungsdauer beeinflusst wurden, wirkten sich auf das Sorptionsverhalten und mechanische Eigenschaften aus. Je nach ausgesetztem Klima und erfolgter Modifikation wurde die Ausgleichsfeuchte der Proben um 10 % bis 40 % reduziert. Die Abnahme der Ausgleichsfeuchte stabilisierte sich im Temperaturbereich von 200 °C bis 220 °C. Die Bruchschlagarbeit des unbehandelten Bambus betrug 3,8 J/cm², die des behandelten nur 1,4 J/cm². Die Bruchschlagarbeit variierte unabhängig von der Modifikation zwischen dem inneren und äußeren Abschnittes innerhalb des Halmquerschnitts. Der Eindruckswiderstand nahm mit der thermischen Behandlung ebenfalls ab. Unbehandelte Proben hatten 47 N/mm², während die modifizierten Proben nur noch 20 N/mm² aufwiesen. Anhand der Ergebnisse und erworbenen Erfahrungen lies sich schlussfolgern, dass Temperaturen zwischen 180 °C und 200 °C bei einer Haltezeit von drei Stunden für die thermische Modifizierung von Äthiopischem Hochlandbambus in Bezug auf die Entwicklung von ”woven strand boards” empfehlenswert waren.