Phenol formaldehyde (PF) resol resins have long been used widely as wood adhesives due to their excellent bonding performance, water resistance and durability. With the growing concern for fossil fuel depletion and climate change, there is a strong interest in exploring renewable biomass materials as substitutes for petroleum-based feedstock. Bark, rich in phenolic compounds, has demonstrated potential to partially substitute phenol in synthesizing bio-based PF resins. In this study, acid-catalyzed phenol liquefaction and alkaline extraction were used to convert mountain pine beetle (MPB; Dendroctonus ponderosae) infested lodgepole pine (Pinus contorta) barks to phenol substitutes, liquefied bark and bark extractives. Two types of bio-based phenol formaldehyde (PF) resol resins, namely liquefied bark-PF resin and bark extractive-PF resins, were then synthesized and characterized. It was found that acid-catalyzed phenol liquefaction and alkaline extraction were effective conversion methods to obtain phenol substitute with the maximum yield of 85% and 68%, respectively. The bio-based PF resol resins had higher molecular weights, higher polydispersity indices, shorter gel times, and faster curing rates than the lab synthesized control PF resin without the bark components. Based on the lap-shear tests, the bio-based PF resol resins exhibited comparable wet and dry bonding strength to lab PF resin and commercial PF resin. The post-curing thermal stability of the bio-based PF resins was similar to the lab control PF resin. The liquid-state 13C nuclear magnetic resonance (NMR) study revealed significant influences on the resin structures by the inclusion of the bark components. Methylene ether bridges, which were absent in the lab PF resin, were found in the bio-based PF resins. The bark components favored the formation of para-ortho methylene linkages in the bio-based bark extractive-PF resins. The liquefied bark-PF resin showed a higher ratio of para-para/ortho-para methylene link (-CH2-), a higher unsubstituted/substituted hydrogen (-H/-CH2OH) ratio and a higher methylol/methylene (-CH2OH/-CH2-) ratio than the bark extractive-PF resin. Both tannin components of bark alkaline extractives and phenolated barks contributed to the acceleration of the curing rate of the bio-based resins. This research demonstrated the promise of the bio-based PF resins containing either bark alkaline extractives or liquefied barks as environmentally friendly alternatives to PF adhesives derived solely from fossil fuel based phenol and proposed a novel higher value-added application of the largely available barks from the mountain pine beetle-infested lodgepole pine trees.

Phenol formaldehyde (PF) resol resins have long been used widely as wood adhesives due to their excellent bonding performance, water resistance and durability. With the growing concern for fossil fuel depletion and climate change, there is a strong interest in exploring renewable biomass materials as substitutes for petroleum-based feedstock. Bark, rich in phenolic compounds, has demonstrated potential to partially substitute phenol in synthesizing bio-based PF resins. In this study, acid-catalyzed phenol liquefaction and alkaline extraction were used to convert mountain pine beetle (MPB; Dendroctonus ponderosae) infested lodgepole pine (Pinus contorta) barks to phenol substitutes, liquefied bark and bark extractives. Two types of bio-based phenol formaldehyde (PF) resol resins, namely liquefied bark-PF resin and bark extractive-PF resins, were then synthesized and characterized. It was found that acid-catalyzed phenol liquefaction and alkaline extraction were effective conversion methods to obtain phenol substitute with the maximum yield of 85% and 68%, respectively. The bio-based PF resol resins had higher molecular weights, higher polydispersity indices, shorter gel times, and faster curing rates than the lab synthesized control PF resin without the bark components. Based on the lap-shear tests, the bio-based PF resol resins exhibited comparable wet and dry bonding strength to lab PF resin and commercial PF resin. The post-curing thermal stability of the bio-based PF resins was similar to the lab control PF resin. The liquid-state 13C nuclear magnetic resonance (NMR) study revealed significant influences on the resin structures by the inclusion of the bark components. Methylene ether bridges, which were absent in the lab PF resin, were found in the bio-based PF resins. The bark components favored the formation of para-ortho methylene linkages in the bio-based bark extractive-PF resins. The liquefied bark-PF resin showed a higher ratio of para-para/ortho-para methylene link (-CH2-), a higher unsubstituted/substituted hydrogen (-H/-CH2OH) ratio and a higher methylol/methylene (-CH2OH/-CH2-) ratio than the bark extractive-PF resin. Both tannin components of bark alkaline extractives and phenolated barks contributed to the acceleration of the curing rate of the bio-based resins. This research demonstrated the promise of the bio-based PF resins containing either bark alkaline extractives or liquefied barks as environmentally friendly alternatives to PF adhesives derived solely from fossil fuel based phenol and proposed a novel higher value-added application of the largely available barks from the mountain pine beetle-infested lodgepole pine trees.

Bio-oil produced from biomass by the fast pyrolysis method is promising as a renewable fuel and as sources of industrial chemicals. In this study, lower cost separation methods of organic acids such as acetic and formic acids and pyrolytic lignin fraction present in bio-oil were investigated to provide basic data needed for future industrial production procedures. The calcium oxide method and a quaternary ammonium anion-exchange resin method were studied to separate organic acids as respective salts and the methanol-and-water method was studied to separate the water-insoluble pyrolytic lignin fraction. The calcium oxide and anion-exchange methods were shown to be effective in separation of organic acids, although further improvements would be needed. The pyrolytic lignin separation method was also shown to give lignin fraction that is effective for up to 40% replacement of phenol in the oriented strand board core-layer binder PF resins.

This work correlates the chemistry of phenol-formaldehyde (PF) resins, its functionalities with their microstructural and mechanical properties in composite materials. The main focus is put on the development of the pores in dependence on the chemical composition of the resins and their influence on the structure of the material. Chemical characteristics of the synthesized resins are analyzed and physical/mechanical properties of the matrices based on PF resins are determined. Differences in the chemical properties are detected e.g. by FT-IR and NMR spectroscopy. They indicate the existence of similar molecular basic structure units, but different network conditions of the resins. DSC investigations point on different reaction mechanisms and temperatures; they reveal also their changed thermal behavior. The bulk matrix behavior differs from that of the composite based on the same resin due to the three dimensional stress and strain fields in the composites. The structure of the CFRP composites is strongly depended on the fiber/matrix interaction. The fiber matrix bonding (FMB) strength controls the load transfer via shear forces and therefore the segmentation of the fiber bundles.

This work correlates the chemistry of phenol-formaldehyde (PF) resins, its functionalities with their microstructural and mechanical properties in composite materials. The main focus is put on the development of the pores in dependence on the chemical composition of the resins and their influence on the structure of the material. Chemical characteristics of the synthesized resins are analyzed and physical/mechanical properties of the matrices based on PF resins are determined. Differences in the chemical properties are detected e.g. by FT-IR and NMR spectroscopy. They indicate the existence of similar molecular basic structure units, but different network conditions of the resins. DSC investigations point on different reaction mechanisms and temperatures; they reveal also their changed thermal behavior. The bulk matrix behavior differs from that of the composite based on the same resin due to the three dimensional stress and strain fields in the composites. The structure of the CFRP composites is strongly depended on the fiber/matrix interaction. The fiber matrix bonding (FMB) strength controls the load transfer via shear forces and therefore the segmentation of the fiber bundles.:1 Introduction 2 Theoretical Overview 2.1 Phenol-Formaldehyde Resins 2.1.1 Overview 2.1.2 Reactions of phenol-formaldehyde resin 2.1.2.1 Addition reaction 2.1.2.2 Condensation reaction 2.1.2.3 Curing 2.1.3 Application of phenol-formaldehyde resin 2.2 Carbon-Fiber 2.2.1 PAN type carbon fiber 2.2.2 Pitch type carbon fiber 2.2.3 Application of carbon fiber 2.3 Composites 2.3.1 Carbon fiber composites 2.3.2 Matrix 2.3.3. Interfaces 2.3.3.1 Carbon fiber side interface between carbon fiber and matrix 2.3.3.2 Matrix side interface between carbon fiber and matrix 2.3.3.3 Toughening of fiber-reinforced polymer 3 Goal and Works 3.1 Problem and Motivation 3.2 Objective and Works plan 4 Experiments and Methods 4.1 Materials 4.1.1 Chemical reagents 4.1.2 Carbon fiber weave 4.2 Synthesis of Resin 4.3 Fabrication of Matrix 4.4. Measurement methods and Experimental approach 4.4.1 Chemical analysis 4.4.2 Microstructure characterization 4.4.3 Mechanical test 5 Chemical characterization of modified phenol-formaldehyde resin 5.1 Fourier Transformed Infrared spectroscopy (FT-IR) 5.1.1 Introduction 5.1.2 Preparation and Measurement 5.1.3 Results and Discussion 5.2 Nuclear Magnetic Resonance spectroscopy (NMR) 5.2.1 Liquid 13C Nuclear Magnetic Resonance spectroscopy 5.2.1.1 Introduction 5.2.1.2 Preparation and Measurement 5.2.1.3 Results and Discussion 5.2.2 Solid 13C CP-MAS Nuclear Magnetic Resonance spectroscopy 5.2.2.1 Introduction 5.2.2.2 Preparation and Measurement 5.2.2.3 Results and Discussion 5.3 Simultaneous Thermal Analysis (STA) 5.3.1 Introduction 5.3.2 Preparation and Measurement 5.3.3 Results and Discussion 5.3.3.1 Simultaneous Thermal Analysis 5.3.3.2 Different Scanning Calorimetry 5.4 Conclusion 6 Microstructural Characterization 6.1 Porosity 6.1.1 Introduction 6.1.2 Preparation and Measurement 6.1.3 Results and Discussion 6.1.3.1 Density 6.1.3.2 Porosity 6.2 Morphology 6.2.1 Introduction 6.2.2 Preparation and Measurement 6.2.3 Results and Discussion 6.2.3.1 Optical Microscopy 6.3.3.2 Scanning Electron Microscopy 6.3.3.2.1 Observation of the bulk matrix 6.2.3.2.2 Structural observation of the composite 6.3 Conclusion 7 Mechanical Properties 7.1 Hardness test 7.1.1 Introduction 7.1.2 Preparation and Measurement 7.1.3 Results and Discussion 7.2 Micro-bending test 7.2.1 Introduction 7.2.2 Preparation and Measurement 7.2.3 Results and Discussion 7.3 Conclusion 8 Summary and Conclusion 8.1 Summary 8.2 Conclusion 9 References