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Phenol formaldehyde (PF) is the oldest known synthetic polymer. This polymer has seen many applications throughout history, including jewelry, electric wire insulation, and resins used to make adhesives. Today, PF resins are still crucial components used in the wood products industry. These PF resins are formulated into adhesives used to make plywood and various other wood composite products. For example, in the United States, 90 % of the homes are still frame homes that use plywood for construction. The PF adhesives used to make these composites are formulated using agricultural waste products like walnut shells and corn-cob residue. These organic waste products act as fillers that reduce the cost, increase the viscosity, and affect the rheology of the fillers. Wheat flour is added as an extender to reduce cost and affect the tack of the adhesive. These organic fillers are lignocellulosic materials that are made of lignin, cellulose, and hemicellulose. Not much is known about the interactions of these organic fillers and the polymer resin. Rheological studies in our lab have shown that not all of the additions to the adhesive formulation are inert components in the adhesive. The steady-state flow curve analysis of PF adhesives revealed that there is a liquid structure change that occurs at high shear rate. This structure change is observed as a viscosity increase that occurs after applying a maximum shear rate of 4000 1/s. A rheological analysis was conducted to determine the source of this change, with individual components added to the resin. The PF base resin (with nothing added) has a Newtonian rheological behavior. When wheat flour is added to the resin, the overall viscosity increases, and shear thinning occurs at highe shear rates. There is no final viscosity change observed on with the addition of wheat flour. Adding corn-cob residue to the resin increased viscosity, led to some shear thinning at higher shear rates, and allowed the viscosity changes observed in the fully formulated adhesives. These experiments showed that the liquid structural changes that occur in the adhesives are attributed to the organic fillers. All organic fillers used in our studies, including corn-cob residue, walnut shell, almond shell, and Alder bark produce different levels of viscosity change in the PF adhesive formulations. These biomass materials have varying amounts of lignocellulosic content, particle size distributions, and particle shape. Among the fillers, corn-cob residue was shown to cause the most viscosity change compared to any of the fillers. Corn-cob residue is unique compared to the others because it has undergone acid digestion to convert its xylans to furfural. During the viscoelastic oscillation studies, the corn-cob residue filled adhesives showed that they developed network structures in response to a high shear rate that were not observed using the other fillers. With the discovery of these network structures, the next goal of this research was to correlate the effects observed on the rheometer to relevant adhesive application technology like high shear spraying. The corn-cob residue adhesive was sprayed at approximately 70,000 1/s compared to the 4000 1/s of rotational shear on the rheometer. The viscoelastic oscillation studies revealed that there was no network structure formation after high-shear spraying. Further, there was no change observed in the flow curve analysis after spraying the adhesive. This study showed that there are limitations when trying to correlate changes that happen in adhesives during spraying, where extensional forces dominate compared to shear forces. In future research, there is the opportunity to explore the effects of extensional deformation that occurs during the atomization of the adhesive, which will be more reflective of the changes that occur during spraying. / Doctor of Philosophy / Phenol-formaldehyde adhesives are crucial products in the home construction industry. These adhesives are used to make plywood that is used to build frame homes, which represent approximately 90 % of the homes in the United States. These phenol-formaldehyde adhesives are made using organic materials repurposed from agricultural waste products like corn cobs, walnut shells, almond shells, and tree bark. These products help to enhance the properties of the adhesive, reduce the cost, and reduce the amount of resin used. The goal of this research is to understand better the interactions between the adhesive and the organic fillers using rheology. Rheology is a field that studies how materials change and flow with applied external forces. This is an important field because it provides information on viscosity and viscoelastic behavior. Our research has shown that in response to high shear rates, the viscosity of these phenol-formaldehyde adhesives increases. Studying these changes can lead to a better understanding of how these materials change during industrial spraying. This understanding could lead to improved building adhesive materials in the home construction industry.

The thesis aims to illustrate and highlight the potential of graphene-based fillers in reinforcing organic coatings deposited by cataphoresis. Thanks to particular surface modification processes of the graphene flakes, these have been properly distributed within the polymer matrix, providing the composite coating with remarkable protective performance. The optimization of the deposition process parameters, as well as the amount of filler, also allowed to improve the mechanical and conductivity properties of the cataphoretic matrix, suggesting the possibility of realizing multifunctional coatings. Finally, these ’smart’ coatings were made by combining two deposition techniques, creating two layers with distinct purposes, containing different types of graphene-based fillers. The cataphoretic primer provided the substrate with high corrosion protection, while the spray top coat possessed high properties of electrical conductivity and resistance to abrasion phenomena. Ultimately, graphene has proven to be an excellent resource as a reinforcing filler in multifunctional organic coatings.

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This was a university/industry research cooperation with focus on how organic fillers affect the properties of phenol-formaldehyde resole (PF) resins that are formulated for veneer applications like plywood and laminated veneer lumber. The PF formulations studied in this work used fillers that were derived from walnut shell (Juglans regia), alder bark (Alnus rubra), almond shell (Prunus dulcis), and corn cob (furfural production) residue. The chemical composition of all fillers was measured and compared to published data. The basic rheological behavior of the formulations was determined and used to develop an adhesive tack measurement based upon lubrication theory. In this work, the probe-tack test was adapted to a typical stress-controlled rheometer by using the normal force and displacement system to compress the adhesive between parallel plates. By employing a simple power law to describe the complex rheology of adhesives and a lubrication approximation for the viscous force, squeeze flow of adhesives between two flat, impermeable steels and between steel and porous wood can be successfully modeled. However, deviations from theory were encountered as related to the method of adhesive application. Both meniscus force in consequence of the surface tension of adhesive pull around the edge of plate and viscous force due to the viscosity of adhesive operate inside the meniscus when adhesive was spread on the entire surface by a hard roller. manufacture where viscosity and surface tension effects were both involved. Last but not Such is probably the case when wood veneer is cold-pressed (pre-pressed) in plywood least, rheological behavior and alkali modification of wheat flour was determined by rheological and infrared studies, respectively. / Master of Science

Veneer-based structural wood composites are typically manufactured using phenol-formaldehyde resols (PF) that are formulated with wheat flour extender and organic filler. Considering that this technology is several decades old, it is surprising to learn that many aspects of the formulation have not been the subject of detailed analysis and scientific publication. The effort described here is part of a university/industry research cooperation with a focus on how the organic fillers impact the properties of the formulated adhesives and adhesive bond performance. The fillers studied in this work are derived from walnut shell (Juglans regia), alder bark (Alnus rubra), and corn cob (furfural production) residue. Alder bark and walnut shell exhibited chemical compositions that are typical for lignocellulosic materials, whereas corn cob residue was distinctly different owing to the high pressure steam digestion used in its preparation. Also, all fillers had low surface energies with dominant dispersive effects. Surface energy of corn cob residue was a little higher than alder bark and walnut shell, which were very similar. All fillers reduced PF surface tension with effects greatest in alder bark and walnut shell. Surface tension reductions roughly correlated to the chemical compositions of the fillers, and probably resulted from the release of surface active compounds extracted from the fillers in the alkaline PF medium. It was shown that viscoelastic network structures formed within the adhesive formulations as a function of shear history, filler type, and filler particle size. Relative to alder bark and walnut shell, the unique behavior of corn cob residue was discussed with respect to chemical composition. Alder bark and walnut shell exhibited similar effects with a decrease of adhesive activation energy. However, corn cob reside caused much higher adhesive activation energy. Alder bark exhibited significant particle size effects on fracture energy and bondline thickness, but no clear size effects on penetration. Regarding corn cob residue and walnut shell, particle size effects on fracture energy were statistically significant, but magnitude of the difference was rather small. Classified corn cob residue fillers all resulted in a similar bondline thickness (statistically no difference) that was different walnut shell. / Ph. D.