Polymeric methylenebis(phenylisocyanate) (pMDI) has increasingly been used in the wood particulate composite industry. Wood composites, especially oriented strand board (OSB) are made with many variations of wood species. Little research has been done to investigate how pMDI adhesion has been affected by species. The present is divided into two parts. First, mode I fracture mechanics and surface free energy analysis was performed to investigate differences in adhesion between southern yellow pine and yellow-poplar bonded with pMDI. Secondly, an improvement in the synthesis of 13C, 15N labeled pMDI is discussed. Mode I fracture results show that pMDI adhesion was affected differently by southern yellow pine compared yellow poplar. The shear energy release rate was significantly higher in pine/pMDI composites than in yellow poplar/pMDI composites. The total surface energy of southern yellow pine was shown to be significantly greater than yellow poplar. The free energy of adhesion (DG) of the pine/pMDI and the poplar/pMDI was investigated. The DG indicated that the pine/pMDI system would take more energy to separate compared to the poplar/pMDI system. Lastly, a double-labeled 13C, 15N pMDI adhesive was successfully synthesized to produce Solid-State NMR composites. / Master of Science

This project addresses two main subjects of moisture-cure polyurethane (PUR) wood adhesives: wood/PUR interactions and structure-property behavior emphasizing on weather durability. For these purposes, one simplified model PUR (MPUR) and three more commercially significant PURs (CPURs) with different hard segment contents were prepared. Separately, an early side project involved the synthesis of a 13C and 15N double-labeled polymeric methylenebis(phenylisocyanate) (pMDI) resin; this was used for the solid-state NMR characterization of isocyanate cure chemistry in wood bondline. MPUR and a CPUR were employed to investigate whether wood/adhesive interactions influence PUR properties. Wood interactions significantly altered PUR hard/soft domain size distribution (atomic force microscopy, AFM), thermal transition temperatures (dynamic mechanical analyses, DMA), and urethane/urea hydrogen bonds (Fourier transform infrared spectroscopy, FTIR). The effects of hard segment content on properties of PUR prepolymers, and cured PURs (films and wood composites) were studied. Hard segment content largely influenced the PURs’ molecular weights, viscosity, penetration, thermal transitions, and hard segment hydrogen bonds, but only slightly altered the dry (unweathered) bondline toughness. Three accelerated weathering procedures were developed to evaluate CPUR bondline weather durability through mode-I fracture testing. Both hard segment content and weathering conditions were found to significantly influence the bondline weather durability. Among these weathering procedures, only one (VPSS) was able to effectively distinguish weather durability of PUR adhesives, and therefore it was selected for detailed structure-weather durability studies. PUR weather durability was found to correlate with its moisture sensitivity and hard segment softening temperature; both were provided by water-submersion DMA. Much attention was directed to the investigation of weather-induced PUR molecular changes. FTIR studies provided evidences of post-cure, hydrolytic degradation, and variation of urethane/urea hydrogen bonds. DMA presented weathering effects on PUR thermal properties. Special efforts have been made to correlate these analytical results with PUR weather durability. A 13C and 15N double-labeled pMDI resin was synthesized and used for solid-state NMR characterization of isocyanate cure chemistry in wood bondline, particularly to detect the evidence of urethane formation. Rotational echo double resonance (REDOR) NMR clearly revealed the formation of urethane linkages, but largely overestimated their content. / Ph. D.

This work describes the development of an improved mode I fracture testing procedure for adhesively-bonded wood, and demonstrates the sensitivity of this approach. The two significant improvements were: 1) the use of the flat double cantilever beam (DCB) geometry, which has been uncommon for wood and 2) the application of an established and powerful data analysis using a corrected compliance method from beam theory. Three studies were conducted using various wood adhesives and DCB specimens were fabricated from yellowpoplar (Liriodendron tulipifera) sapwood. The sensitivity of this methodology showed significant differences in fracture performance as the degree of cure increased for a phenol formaldehyde adhesive, and yielded maximum strain energy release rate (SERR) values of 370 - 560 J/m2. A second study showed performance differences between two polymeric diphenylmethane diisocyanate (pMDI) adhesives and one polyurethane adhesive. Typical maximum SERR values were 160 and 130 J/m2 for the pMDI adhesives and 160 J/m2 for the polyurethane adhesive. A third study investigated the effect of loading rates on a cross-linked polyvinyl acetate adhesive and maximum SERR values of 370 - 560 J/m2 were achieved. Adhesive penetration and cure were determined by image analysis with fluorescence microscopy, and by micro-dielectric analysis, respectively. Since the geometry of the fracture procedure dictates the absence of wood failure, the resulting fractured surfaces were readily analyzable. The surface analysis techniques of laser ionization mass analysis, solid-state nuclear magnetic resonance and field emission scanning electron microscopy were used to investigate the locus of failure for the smooth fractured surfaces. / Master of Science

This work included two separate studies; the common theme in each was the use of mode-I fracture testing to evaluate wood adhesion. In the first study, mode-I fracture testing was used to compare the thermal stability of polyurethane (PUR) and resorcinol-formaldehyde (RF) wood adhesives. Bonded specimens for both adhesives were subjected to prolonged thermal exposure, and fracture testing was subsequently conducted after re-equilibration to standard test conditions. It was found that both PUR and RF suffered a significant fracture energy loss after heat treatment, and that RF was more thermally stable than PUR, as expected. However, both adhesives suffered significant thermal degradation, and fracture testing did not distinguish the RF system as being clearly superior to PUR. Dynamic mechanical analysis (DMA) was also used to analyze and compare the thermal softening of PUR and RF in terms of the decline in storage modulus. DMA results indicated that PUR specimens suffered greater stiffness loss due to simple thermal softening. Because fracture testing indicated that both adhesives suffered significant degradation, the DMA results suggested that the generally superior fire resistance of RF adhesives is born from greater high temperature stiffness; whereas the more compliant PUR suffers greater immediate softening during thermal exposure. In other words, both systems suffer from thermal degradation, but the more highly cross-linked RF system suffers less thermal softening and therefore maintains a greater load carrying capacity during fire exposure. In the second study, mode-I fracture testing was used to test the effects of wood surface thermal deactivation (surface energy reduction) on the adhesion between southern pine wood (Pinus spp.) and polyethylene (PE). Pine specimens were progressively surface deactivated by 185°C heat treatments for periods of 5, 15, and 60 minutes. Control and deactivated pine laminae were subsequently hotpressed/bonded using PE film as the adhesive. Mode-I fracture testing was conducted under the assumption of linear elasticity, however load/displacement test curves suffered from a severe degree of nonlinearity believed to be caused by PE bridging behind the advancing crack tip. Instead of applying a nonlinear data analysis, a standard linear elastic analysis was conducted and deemed acceptable for comparative purposes within this study. Under dry conditions (unweathered specimens), 5 and 15 minute thermal treatments resulted in progressively worse adhesion (lower fracture energies) when compared to control surfaces; but the 60 minute heat treatment improved adhesion relative to 5 and 15 minute treatments, and showed a trend of improving adhesion as surface deactivation became more extreme. Simulated-weather resistance was also studied and it was determined that the highest degree of surface deactivation slightly improved weather durability in comparison to control surfaces. Overall, the findings here were similar to those in a previously published work- thermal deactivation of wood surfaces shows promise as a method to improve adhesion between wood and nonpolar polyolefins. / 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.

The controlled degradation of wood surfaces with infrared light from a CO2 pulsed laser facilitated adhesion without the use of additional resins. Laser modification creates a surface phenomenon that physically and chemically alters the natural biopolymer organization of lignocellulosic materials in a way that promotes adhesion when hot pressed using typical industrial equipment. Laser optimization was determined through mechanical and microscopic observation. It was determined that a mild level of laser surface modification (scale of 30 W/mm2) resulted in the highest bond-line strength. The large spot size of the laser beam resulted in evenly modified surfaces. Surface analysis revealed that laser modification changed native wood morphology, hydrolyzed and vaporized hemicellulose, and enriched the surface with cellulose II and lignin. Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR FTIR) was used to analyze the bulk of the laser material. This experiment revealed a change in the hydroxyl region related to hydrogen bonding conformations between wood polymers, mainly cellulose. X-ray photoelectron spectroscopy (XPS) provided an elemental composition of the top 5 nanometers of the surface, which resulted in increased carbon-carbon/carbon-hydrogen linkages and decreased oxygen containing bonds due to laser ablation. Static acid-base contact angle analysis was conducted using three probe liquids to find the Lewis acid, Lewis base, and dispersion components of the top nanometer of surface chemistry. Contact angle analysis revealed laser modified samples had a surface free energy that remained similar to the control wood sample. In addition, the dispersion component of the surface free energy increased due to laser ablation while acid-base components were reduced. Atomic force microscopy (AFM) visually displays a reduction in surface roughness due to the laser technique. An additional set of experiments like thermal gravimetric analysis, thermal pre and post treatments, and heated ATR FTIR and XPS support findings which require more investigation into this adhesion phenomenon. / Master of Science

Phenol-formaldehyde (PF) resole and polymeric diphenylmethane diisocyanate (PMDI) are two commonly used exterior thermosetting adhesives in the wood-based composites industry. There is an interest in combining these two adhesives in order to benefit from their positive attributes while also neutralizing some of the negative ones. Although this novel adhesive system has been reportedly utilized in some limited cases, a fundamental understanding is lacking. This research serves this purpose by investigating some of the important aspects of this novel adhesive system. The adhesive rheological and viscometric properties were investigated with an advanced rheometer. The resole/PMDI blends exhibited non-Newtonian flow behavior. The blend viscosity and stability were dependent on the blend ratio, mixing rate and time. The adhesive penetration into wood was found to be dependent on the blend ratio and correlated with the blend viscosity. By using dynamic mechanical analysis, the blend cure speed was found to increase with the PMDI content. Mode I fracture testing of resole/PMDI hybrid adhesive bonded wood specimens indicated the dependence of bondline fracture energy on the blend ratio. The 75/25 PF/PMDI blend exhibited a high fracture energy with a fast cure speed and processable viscosity. Exposure to water-boil weathering severely deteriorated the fracture energies of the hybrid adhesive bondlines. More detailed chemistry and morphological studies were performed with cross-polarization nuclear magnetic resonance and 13C, 15N-doubly labeled PMDI. A spectral decomposition method was used to obtain information regarding chemical species concentration and relaxation behavior of the contributing components within the major nitrogen resonance. Different urethane concentrations were present in the cured blend bondlines. Water-boil weathering and thermal treatment at elevated temperatures (e.g. > 200°C) caused reduced urethane concentrations in the bondline. Solid-state relaxation parameters revealed a heterogeneous structure in the non-weathered blends. Water boil weathering caused a more uniform relaxation behavior in the blend bondline. By conducting this research, more fundamental information regarding the PF/PMDI hybrid adhesives will become available. This information will aid in the evaluation of, and improve the potential use of PF/PMDI hybrid adhesives for wood-based composites. / Ph. D.

Water-based resol phenol formaldehyde, PF, and organic polymeric methylenebis(phenylisocyanate), pMDI, are the two primary choices for the manufacture of exterior grade wood-based composites. This work addresses simple physical blends of pMDI dispersed in PF as a possible hybrid wood adhesive. Part one of this study examined the morphology of hybrid blends prepared using commercially available PF and pMDI. It was found that the blend components rapidly reacted such that the dispersed pMDI droplets became encased in a polymeric membrane. The phase separation created during liquid/liquid blending appeared to have been preserved in the cured, solid-state. However, substantial interdiffusion and copolymerization between blend components also appeared to have occurred according to measured cure rates, dynamic mechanical analysis, and atomic force microscopy. In the second part of this study a series of PF resins was synthesized employing the so-called "split-cook" method, and by using a range of formaldehyde/phenol and NaOH/phenol mole ratios. These neat PF resins were subjected to the following analyses: 1) steady-state flow viscometry, 2) free formaldehyde titration, 3) non-volatile solids determination, 4) size exclusion chromatography, 5) quantitative solution-state ¹³C nuclear magnetic resonance, NMR, 6) differential scanning calorimetry, 7) parallel-plate oscillatory cure rheology, and 8) dielectric spectroscopy. The neat PF analytical results were unremarkable with one exception; NMR revealed that the formaldehyde/phenol mole ratio in one resin substantially differed from the target mole ratio. The neat PF resins were subsequently used to prepare of series of PF/pMDI blends in a ratio of 75 parts PF solids to 25 parts pMDI solids. The resulting PF/pMDI blends were subjected to the following analyses: 1) differential scanning calorimetry, 2) parallel-plate oscillatory cure rheology, and 3) dielectric spectroscopy. Similar to what was inferred in part one of this study, both differential scanning calorimetry (DSC) and oscillation cure rheology demonstrated that cure of the PF continuous phase was substantially altered and accelerated by pMDI. However within actual wood bondlines, dielectric analysis detected little variation in cure speed between any of the formulations, both hybrid and neat PF. Furthermore, the modulated DSC curing experiments detected some latent reactivity in the hybrid system, both during initial isothermal curing and subsequent thermal scanning. The latent reactivity may suggest that a significant diffusion barrier existed between blend components, preventing complete reaction of hybrid blends even after thermal scanning up to 200 °C. Part three of this work examined the bonded wood mode-I fracture performance of hybrid resins as a function of the resol formaldehyde/phenol ratio and also the alkali content. A moderate increase in unweathered fracture toughness was observed for hybrid formulations relative to neat PF. Following accelerated weathering, the durability of the hybrid blends was promising: weathered hybrid toughness was equivalent to that of weathered neat PF. While the resol F/P ratio and alkali content both influenced hybrid fracture toughness, statistical modeling revealed interaction between these variables that complicated result interpretation: the influence of hybrid alkali content depended heavily on each formulation's specific F/P ratio, and vice versa. / Master of Science

The global progression towards sustainable energy, materials and chemicals requires novel and improved analytical tools to understand and optimize lignocellulosic biomass utilization. In an effort to advance lignocellulose characterization, gain insights into biomass processing, and obtain novel perspectives on cell wall ultrastructure, this study utilizes three principal polymer characterization techniques, namely compressive-torsion dynamic mechanical analysis (DMA), deuterium quadrupolar nuclear magnetic resonance (2H NMR) and rheo-infrared spectroscopy. A novel parallel-plate compressive-torsion DMA protocol is developed to analyze very small solvent-plasticized biomass specimens with or without mechanical integrity. The benefits and limitations of this technique are demonstrated by comparing it to a conventional tensile-torsion DMA while analyzing various solvent-plasticized lignocelluloses. The rheology of wood in various organic solvents is studied through dynamic thermal scans, Time/temperature superposition (TTS) and fragility analysis. Plasticizing solvents and wood grain orientation significantly affected the lignin glass-transition temperature. Dynamic TTS reveals that while all storage modulus data shift smoothly, the thermorheological complexity of solvent-plasticized wood becomes evident in loss component master curves. It is argued that the plasticized lignocellulose TTS is insightful and potentially useful, although it fails to satisfy the classic TTS validity criteria. Subsequently, it is justified that the fragility analysis is a better suited treatment than the WLF model to investigate cooperative segmental motions of plasticized wood. Deuterium quadrupolar NMR reveals a new perspective on the orientation of amorphous wood polymers and two distinct amorphous polymer domains: a highly oriented phase in the S2 layer of the secondary cell wall and an isotropic phase postulated to occur in the compound middle lamella (CML). If the origin of the isotropic phase is confirmed to arise from the CML, then this technique provides a way to independently investigate the morphology and phase dynamics of CML and S2 in an intact tissue, and should bring novel insights into deconstructive strategies specific to the oriented and unoriented domains. Finally the effects of a wood-adhesion promoter (hydroxymethyl resorcinol, HMR) on in-situ wood polymers are studied to elucidate the still unresolved HMR-lignocellulose interactions. DMA, creep-TTS and 2H NMR reveal that HMR increases the crosslink density and restricts the mobility of wood amorphous phase. Rheo-IR spectroscopy shows that the molecular stress-transfer mechanism is altered within the wood cell wall. / Ph. D.

The primary direction of this thesis was towards exploring qualitative and quantitative characteristics necessary for refining and understanding the flat wood double cantilever beam (DCB) as a valid means for testing Mode I fracture energy in wood adhesive bonds. Southern yellow pine (SYP) adherends were used with epoxy and phenol formaldehyde (PF) impregnated films, providing two systems with different characteristics for investigation. An adhesive penetration analysis was performed for both the epoxy and PF bonds. The PF penetration into the SYP was shown to be relatively shallow. The epoxy penetration was shown to be deeper. Epoxy-SYP DCBs were quasi-statically tested with varying widths (10 mm, 15 mm, and 20 mm), showing decreases in scatter of critical and arrest strain energy release rates, GIc and GIa, with increases in specimen width. Quasi-static fracture testing was also performed on PF SYP-DCBs, showing much higher critical and arrest fracture energy values than the epoxy-SYP DCBs, indicating that deep adhesive penetration is not necessarily a requisite for higher Mode I fracture energy values. Grain distribution influences were computationally investigated because of the stiffness difference between latewood and earlywood growth and the grain angle along the length of the beams. The grain angle and the stiffness difference between latewood and earlywood growth caused the effective stiffness, (ExxI)eff, to vary along the length of the beam. The effective stiffness variation caused variations in the beam's ability to receive and store strain energy, complicating and confounding determination of experimental results. Cyclic loading tests were performed on PF-SYP DCB's. The cycle frequency was 3Hz, with a valley to peak load ratio of R = 0.5. Specimen softening was observed with cycling, with re-stiffening occurring with crack growth. Contrary to expectations, specimen compliance occasionally decreased with small crack extensions. A toughening mechanism was frequently observed, whereby subsequent crack lengths required more cycles to failure than the previous crack length. Monotonically extending the crack length far from the fatigued region created a fresh crack that did not show the toughened behavior. But toughening did resume with subsequent crack lengths. / Master of Science