Improving the fire retardancy of extruded/coextruded wood-plastic composites

The main objective of this thesis is to study the impact of different mineral fillers and fire retardants on the reaction-to-fire properties of extruded/coextruded wood-plastic composites (WPCs). The impact of additives on the flammability properties of WPCs is studied by cone calorimetry. The studied properties are ignition time, peak heat release rate, total heat release, total smoke production, and mass loss rate. The effects of mineral fillers and fire retardants were found to vary with the type of additive, the type of additive combinations, the amount of additives, as well as the production method of the WPCs. The study shows that talc can be used to improve the properties of extruded WPCs. Especially ignition time, peak heat release rate and mass loss rate were found to be improved significantly by talc. The most significant improvement in the fire retardancy of coextruded WPCs was achieved in combinations of natural graphite and melamine. Ignition time, peak heat release rate and total smoke production were improved essentially. High increase in smoke production was found in samples where the amount of ammonium polyphosphate was 10% or higher. Coextrusion as a structural modification was found as a promising way to improve the flammability properties of composite materials in a cost-effective way.

Estudo das características de adsorção de água e da estabilidade das microcápsulas de óleo essencial de laranja na seleção de material de parede

Este trabalho consistiu no estudo e comparação das características de adsorção de água de três amostras de microcápsulas de óleo essencial de laranja, obtidas pela secagem por atomização de três diferentes emulsões preparadas pela adição de óleo essencial de laranja (oel), a uma solução aquosa de material de parede (mp) constituída de capsul (5,0, 0,0 e 10,0%), goma arábica (5,0, 10,0 e 0,0%) sendo constante para as três emulsões a maltodextrina (36,0%), água (44,0%) e óleo essencial (10,0%). A microencapsulação foi realizada a 220 e 110° C de ar de entrada e saída do secador usando um atomizador rotativo a 20.000rpm. Com base à determinação das isotermas de adsorção de água a 30, 40 e 50° C e usando o modelo de GAB para ajustar os pontos experimentais foram avaliadas as características das isotermas, a estabilidade e área superficial de adsorção de água das diferentes amostras de microcápsulas obtidas. Os resultados indicaram ser importante o estudo das características de adsorção de água para estimar a estabilidade das microcápsulas de oel e a comparação destas mostrou que as microcápsulas obtidas pela secagem por atomização da emulsão preparada com 5,0% de capsul e 5,0% de goma arábica apresentaram o melhor resultado.

Microencapsulação de óleo essencial de laranja: seleção de material de parede

No presente trabalho se procedeu à comparação de agentes microencapsulantes, material de parede (mp), na microencapsulação de óleo essencial de laranja (material ativo) através da secagem por atomização. Foram preparadas três amostras de emulsões pela adição de óleo essencial de laranja a uma solução aquosa do mp composta de capsul (5,0, 0,0 e 10,0%), goma arábica (5,0, 10,0 e 0,0%) sendo constante para as três amostras maltodextrina (36,0%), água (44,0%) e óleo essencial (10,0%). Foram avaliadas as curvas de secagem das emulsões frente à retenção do óleo essencial de laranja e a tendência de formação de dobras superficiais das partículas e verificou-se a hipótese "menor a tendência de formação de dobras na superfície das microcápsulas maior a retenção de material ativo". A microencapsulação foi obtida pela secagem por atomização, com temperaturas de 220ºC e 110ºC do ar de entrada e de saída da câmara de secagem, respectivamente, e com atomizador rotativo (20.000rpm). A comparação das microcápsulas obtidas a partir das três amostras de emulsões mostrou que aquela preparada com 10,0% de capsul e 0,0% de goma arábica apresentou o maior resultado. O período de taxa constante de secagem desta mistura é curto e com maior retenção de umidade após a secagem. As microcápsulas obtidas apresentaram maior retenção de óleo essencial e dobras superficiais menos pronunciadas decorrentes do menor entumescimento das gotículas durante a secagem.

Capillary electrophoresis: Applicability and method validation for biorefinery analytics

Wood-based bioprocesses present one of the fields of interest with the most potential in the circular economy. Expanding the use of wood raw material in sustainable industrial processes is acknowledged on both a global and a regional scale. This thesis concerns the application of a capillary zone electrophoresis (CZE) method with the aim of monitoring wood-based bioprocesses. The range of detectable carbohydrate compounds is expanded to furfural and polydatin in aquatic matrices. The experimental portion has been conducted on a laboratory scale with samples imitating process samples. This thesis presents a novel strategy for the uncertainty evaluation via in-house validation. The focus of the work is on the uncertainty factors of the CZE method. The CZE equipment is sensitive to ambient conditions. Therefore, a proper validation is essential for robust application. This thesis introduces a tool for process monitoring of modern bioprocesses. As a result, it is concluded that the applied CZE method provides additional results to the analysed samples and that the profiling approach is suitable for detecting changes in process samples. The CZE method shows significant potential in process monitoring because of the capability of simultaneously detecting carbohydrate-related compound clusters. The clusters can be used as summary terms, indicating process variation and drift.

Utilization of recycled mineral wool as filler in wood plastic composites

The impact of a recycled mineral wool filler on the various properties of wood plastic composites was studied and the critical factors affecting the formation of the properties were determined. An estimation of the volume of mineral wool fiber waste generated in the European Union between the years 2010-2020 was presented. Furthermore, the effect of fiber pre-treatment on the properties of the wood plastic composites were studied, and the environmental performance of a wood plastic composite containing recycled mineral fibers was assessed. The results showed that the volumes of construction and demolition waste and new mineral wool produced in the European Union are growing annually, and therefore also the volumes of recycled mineral wool waste generated are increasing. The study showed that the addition of recycled mineral wool into composites can enhance some of the mechanical properties and increase the moisture resistance properties of the composites notably. Recycled mineral wool as a filler in wood plastic composites can also improve the fire resistance properties of composites, but it does not protect the polymer matrix from pyrolysis. Fiber pre-treatment with silane solution improved some of the mechanical properties, but generally the use of maleated polypropylene as the coupling agent led to better mechanical and moisture resistance properties. The environmental performance of recycled mineral wool as the filler in wood plastic composites was superior compared to glass fibers. According to the findings, recycled mineral wool fibers can provide a technically and environmentally viable alternative to the traditional inorganic filler materials used in wood plastic composites.

Monolithic zirconium dioxide as a full contour restorative material: With special emphasis on the optical and mechanical properties

Full contour monolithic zirconia restorations have shown an increased popularity in the dental field over the recent years, owing to its mechanical and acceptable optical properties. However, many features of the restoration are yet to be researched and supported by clinical studies to confirm its place among the other indirect restorative materials This series of in vitro studies aimed at evaluating and comparing the optical and mechanical properties, light cure irradiance, and cement polymerization of multiple monolithic zirconia material at variable thicknesses, environments, treatments, and stabilization. Five different monolithic zirconia materials, four of which were partially stabilized and one fully stabilized were investigated. The optical properties in terms of surface gloss, translucency parameter, and contrast ratio were determined via a reflection spectrophotometer at variable thicknesses, coloring, sintering method, and after immersion in an acidic environment. Light cure irradiance and radiant exposure were quantified through the specimens at variable thicknesses and the degree of conversion of two dual-cure cements was determined via Fourier Transform Infrared spectroscopy. Bi-axial flexural strength was evaluated to compare between the partially and fully stabilized zirconia prepared using different coloring and sintering methods. Surface characterization was performed using a scanning electron microscope and a spinning disk confocal microscope. The surface gloss and translucency of the zirconia investigated were brand and thickness dependent with the translucency values decreasing as the thickness increased. Staining decreased the translucency of the zirconia and enhanced surface gloss as well as the flexural strength of the fully stabilized zirconia but had no effect on partially stabilized zirconia. Immersion in a corrosive acid increased surface gloss and decreased the translucency of some zirconia brands. Zirconia thickness was inversely related to the amount of light irradiance, radiant exposure, and degree of monomer conversion. Type of sintering furnace had no effect on the optical and mechanical properties of zirconia. Monolithic zirconia maybe classified as a semi-translucent material that is well influenced by the thickness, limiting its use in the esthetic zones. Conventional acid-base reaction, autopolymerizing and dual-cure cements are recommended for its cementation. Its desirable mechanical properties give it a high potential as a restoration for posterior teeth. However, close monitoring with controlled clinical studies must be determined before any definite clinical recommendations can be drawn.

Preparação de um material de referência certificado para controle de agrotóxicos em hortifrutigranjeiros: estudo da homogeneidade

Neste trabalho são apresentados os esforços para garantir a homogeneidade de um material de referência. Níveis residuais (mg.kg-1) de quatro agrotóxicos (γ-HCH, fenitrotiona, clorpirifós e procimidona) foram adicionados à polpa de tomate com o objetivo de se preparar um material de referência certificado. As propriedades mais importantes desses materiais são a homogeneidade e a estabilidade. Antes de serem enviados a outros laboratórios, os materiais de referência precisam ter sua homogeneidade verificada. Nas etapas prévias, amostras foram avaliadas de modo a prover dados sobre o tratamento mais adequado para minimizar a variabilidade analítica do lote preparado e garantir a qualidade da amostra candidata a material de referência certificado, tão bem como a estimativa da incerteza associada à homogeneidade. A análise de variância fornece informações sobre a variabilidade do lote preparado e o grau de invariabilidade da amostra fortificada. Depois da preparação, as amostras foram expostas à radiação gama na dose de 2 kGy e submetidas a um estudo interlaboratorial para certificação. As concentrações certificadas dos agrotóxicos após caracterização foram 0,191 ± 0,047 mg.kg-1; 0,192 ± 0,068 mg.kg-1; 0,225 ± 0,076 mg.kg-1e 0,177 ± 0,051 mg.kg-1 para o γ-HCH, a fenitrotiona, clorpirifós e procimidona respectivamente.

Preparação de um material de referência certificado para controle de agrotóxicos em hortifrutigranjeiros: estudo da estabilidade

Neste trabalho são apresentados os resultados dos estudos de estabilidade referentes à produção de um material de referência certificado. Foram avaliados níveis residuais de concentração dos agrotóxicos γ-HCH, fenitrotiona, clorpirifós e procimidona em polpa de tomate. A pasteurização e a irradiação gama foram empregadas à polpa de tomate, visando manter a integridade da amostra candidata a material de referência. A polpa foi preparada e dividida em duas partes. Cada parte foi fortificada com os referidos agrotóxicos na faixa de concentração de 0,1 a 0,2 mg.kg-1. Uma das partes foi submetida à pasteurização a 90 °C por 4 minutos e a outra parte foi irradiada com dose de 2,0 kGy depois de homogeneizada. A estabilidade e a incerteza da amostra, correspondente ao período de tempo avaliado, foram determinadas através da análise de regressão em conjunto com a ANOVA. Os resultados indicaram que ambos os procedimentos de preparo da amostra são adequados para a conservação da polpa de tomate fortificada com os quatro agrotóxicos, com vantagem para o tratamento por irradiação com a dose de 2,0 kGy.

Microparticles obtained by complex coacervation: influence of the type of reticulation and the drying process on the release of the core material

Microparticles obtained by complex coacervation were crosslinked with glutaraldehyde or with transglutaminase and dried using freeze drying or spray drying. Moist samples presented Encapsulation Efficiency (%EE) higher than 96%. The mean diameters ranged from 43.7 ± 3.4 to 96.4 ± 10.3 µm for moist samples, from 38.1 ± 5.36 to 65.2 ± 16.1 µm for dried samples, and from 62.5 ± 7.5 to 106.9 ± 26.1 µm for rehydrated microparticles. The integrity of the particles without crosslinking was maintained when freeze drying was used. After spray drying, only crosslinked samples were able to maintain the wall integrity. Microparticles had a round shape and in the case of dried samples rugged walls apparently without cracks were observed. Core distribution inside the particles was multinuclear and homogeneous and core release was evaluated using anhydrous ethanol. Moist particles crosslinked with glutaraldehyde at the concentration of 1.0 mM.g-1 protein (ptn), were more efficient with respect to the core retention compared to 0.1 mM.g-1 ptn or those crosslinked with transglutaminase (10 U.g-1 ptn). The drying processes had a strong influence on the core release profile reducing the amount released to all dry samples

Influence of thermal treatment of wood on the aroma of a sugar cane spirit (cachaça) model-solution

The aging process of alcoholic beverages is generally conducted in wood barrels made with species from Quercus sp. Due to the high cost and the lack of viability of commercial production of these trees in Brazil, there is demand for new alternatives to using other native species and the incorporation of new technologies that enable greater competitiveness of sugar cane spirit aged in Brazilian wood. The drying of wood, the thermal treatment applied to it, and manufacturing techniques are important tools in defining the sensory quality of alcoholic beverages after being placed in contact with the barrels. In the thermal treatment, several compounds are changed by the application of heat to the wood and various studies show the compounds are modified, different aromas are developed, there is change in color, and beverages achieve even more pleasant taste, when compared to non-treated woods. This study evaluated the existence of significant differences between hydro-alcoholic solutions of sugar cane spirits elaborated from different species of thermo-treated and non-treated wood in terms of aroma. An acceptance test was applied to evaluate the solutions preferred by tasters under specific test conditions.

Functionalisation of spruce O-acetyl-galactoglucomannans for barrier and composite applications

The increasing use of energy, food, and materials by the growing population in the world is leading to the situation where alternative solutions from renewable carbon resources are sought after. The growing use of plastics depends on the raw-oil production while oil refining are politically governed and required for the polymer manufacturing is not sustainable in terms of carbon footprint. The amount of packaging is also increasing. Packaging is not only utilising cardboard and paper, but also plastics. The synthetic petroleum-derived plastics and inner-coatings in food packaging can be substituted with polymeric material from the renewable resources. The trees in Finnish forests constitute a huge resource, which ought to be utilised more effectively than it is today. One underutilised component of the forests is the wood-derived hemicelluloses, although Spruce Oacetyl-galactoglucomannans (GGMs) have previously shown high potential for material applications and can be recovered in large scale. Hemicelluloses are hydrophilic in their native state, which restrains the use of them for food packaging as non-dry item. To cope with this challenge, we intended to make GGMs more hydrophobic or amphiphilic by chemical grafting and consequently with the focus of using them for barrier applications. Methods of esterification with anhydrides and cationic etherification with a trimethyl ammonium moiety were established. A method of controlled synthesis to obtain the desired properties by the means of altering temperature, reaction time, the quantity of the reagent, and even the solvent for purification of the products was developed. Numerous analytical tools, such as NMR, FTIR, SEC-MALLS/RI, MALDI-TOF-MS, RP-HPLC and polyelectrolyte titration were used to evaluate the products from different perspectives and to acquire parallel proofs of their chemical structure. Modified GGMs with different degree of substitution and the correlating level of hydrophobicity was applied as coatings on cartonboard and on nanofibrillated cellulose-GGM films to exhibit barrier functionality. The water dispersibility in processing was maintained with GGM esters with low DS. The use of chemically functionalised GGM was evaluated for the use as barriers against water, oxygen and grease for the food packaging purposes. The results show undoubtedly that GGM derivatives exhibit high potential to function as a barrier material in food packaging.

Presence of central nervous system tissues as bovine spongiform encephalopathy specified risk material in Turkish raw meat ball (cig kofte)

Abstract Bovine Spongiform Encephalopathy (BSE) is a virulent disease which may infect by affecting the central nervous system (CNS) tissues in cattle and causes degeneration in nerves. Central nervous system tissues such as brain and spinal cord which are classified as specified risk materials (SRMs) are regarded to be main source of infection. The contamination of the meat with the specific risk materials (SRMs) can occur in phases of slaughter, fragmentation of carcass and processing. This study was conducted in order to investigate the existence of CNS tissues in raw meat ball (cig kofte) which is commonly consumed in the Southeastern Region of Turkey, particularly in Şanlıurfa. For this purpose, 145 samples of raw meat ball were tested. The enzyme-linked immunosorbent assay (ELISA) kits (Ridascreen risk material 10/5, R-biofarm GmbH) which determine glial fibrillary acidic protein (GFAP) as determinant were used. As a result of the analyses, positivity was detected in 21 of totally 145 samples of raw meat ball (14.48%). 6 (4.14%) of the samples gave low level of positivity (≥ 0.1 standard absorbance), 10 (6.90%) gave medium level of positivity (>0.2 standard absorbance) and 5 (3.45%) gave high level of positivity (≥0.5 standard absorbance). As a consequence, meats are contaminated in any phase of both slaughter and meat production even if accidentally. Regarding this matter, necessary measures should be taken and hygiene rules should be applied.

Simulation and material calibration of ultra high strength steel (UHSS) S960 welded joint under static tensile test utilizing finite element method (FEM)

The aim of this work was to calibrate the material properties including strength and strain values for different material zones of ultra-high strength steel (UHSS) welded joints under monotonic static loading. The UHSS is heat sensitive and softens by heat due to welding, the affected zone is heat affected zone (HAZ). In this regard, cylindrical specimens were cut out from welded joints of Strenx® 960 MC and Strenx® Tube 960 MH, were examined by tensile test. The hardness values of specimens’ cross section were measured. Using correlations between hardness and strength, initial material properties were obtained. The same size specimen with different zones of material same as real specimen were created and defined in finite element method (FEM) software with commercial brand Abaqus 6.14-1. The loading and boundary conditions were defined considering tensile test values. Using initial material properties made of hardness-strength correlations (true stress-strain values) as Abaqus main input, FEM is utilized to simulate the tensile test process. By comparing FEM Abaqus results with measured results of tensile test, initial material properties will be revised and reused as software input to be fully calibrated in such a way that FEM results and tensile test results deviate minimum. Two type of different S960 were used including 960 MC plates, and structural hollow section 960 MH X-joint. The joint is welded by BöhlerTM X96 filler material. In welded joints, typically the following zones appear: Weld (WEL), Heat affected zone (HAZ) coarse grained (HCG) and fine grained (HFG), annealed zone, and base material (BaM). Results showed that: The HAZ zone is softened due to heat input while welding. For all the specimens, the softened zone’s strength is decreased and makes it a weakest zone where fracture happens while loading. Stress concentration of a notched specimen can represent the properties of notched zone. The load-displacement diagram from FEM modeling matches with the experiments by the calibrated material properties by compromising two correlations of hardness and strength.

The feasibility of torrefaction for the co-firing of wood in pulverised-fuel boilers

Torrefaction is the partial pyrolysis of wood characterised by thermal degradation of predominantly hemicellulose under inert atmosphere. Torrefaction can be likened to coffee roasting but with wood in place of beans. This relatively new process concept makes wood more like coal. Torrefaction has attracted interest because it potentially enables higher rates of co-firing in existing pulverised-coal power plants and hence greater net CO2 emission reductions. Academic and entrepreneurial interest in torrefaction has sky rocketed in the last decade. Research output has focused on the many aspects of torrefaction – from detailed chemical changes in feedstock to globally-optimised production and supply scenarios with which to sustain EU emission-cutting directives. However, despite its seemingly simple concept, torrefaction has retained a somewhat mysterious standing. Why hasn’t torrefied pellet production become fully commercialised? The question is one of feasibility. This thesis addresses this question. Herein, the feasibility of torrefaction in co-firing applications is approached from three directions. Firstly, the natural limitations imposed by the structure of wood are assessed. Secondly, the environmental impact of production and use of torrefied fuel is evaluated and thirdly, economic feasibility is assessed based on the state of the art of pellet making. The conclusions reached in these domains are as follows. Modification of wood’s chemical structure is limited by its naturally existing constituents. Consequently, key properties of wood with regards to its potential as a co-firing fuel have a finite range. The most ideal benefits gained from wood torrefaction cannot all be realised simultaneously in a single process or product. Although torrefaction at elevated pressure may enhance some properties of torrefied wood, high-energy torrefaction yields are achieved at the expense of other key properties such as heating value, grindability, equilibrium moisture content and the ability to pelletise torrefied wood. Moreover, pelletisation of even moderately torrefied fuels is challenging and achieving a standard level of pellet durability, as required by international standards, is not trivial. Despite a reduced moisture content, brief exposure of torrefied pellets to water from rainfall or emersion results in a high level of moisture retention. Based on the above findings, torrefied pellets are an optimised product. Assessment of energy and CO2-equivalent emission balance indicates that there is no environmental barrier to production and use of torrefied pellets in co-firing. A long product transport distance, however, is necessary in order for emission benefits to exceed those of conventional pellets. Substantial CO2 emission reductions appear possible with this fuel if laboratory milling results carry over to industrial scales for direct co-firing. From demonstrated state-of-the-art pellet properties, however, the economic feasibility of torrefied pellet production falls short of conventional pellets primarily due to the larger capital investment required for production. If the capital investment for torrefied pellet production can be reduced significantly or if the pellet-making issues can be resolved, the two production processes could be economically comparable. In this scenario, however, transatlantic shipping distances and a dry fuel are likely necessary for production to be viable. Based on demonstrated pellet properties to date, environmental aspects and production economics, it is concluded that torrefied pellets do not warrant investment at this time. However, from the presented results, the course of future research in this field is clear.