David P. Harper

Acetylation of Cellulose Nanowhiskers with Vinyl Acetate under Moderate Conditions

A novel and straightforward method for the surface acetylation of cellulose nanowhiskers by transesterification of vinyl acetate is proposed. The reaction of vinyl acetate with the hydroxyl groups of cellulose nanowhiskers obtained from cotton linters was examined with potassium carbonate as catalyst. Results indicate that during the first stage of the reaction, only the surface of the nanowhiskers was modified, while their dimensions and crystallinity remained unchanged. With increasing reaction time, diffusion mechanisms controlled the rate, leading to nanowhiskers with higher levels of acetylation, smaller dimensions, and lower crystallinity. In THF, a solvent of low polarity, the suspensions from modified nanowhiskers showed improved stability with increased acetylation.

Adhesive penetration of wood cell walls investigated by scanning thermal microscopy (SThM)

Abstract Cross sections of wood adhesive bonds were studied by scanning thermal microscopy (SThM) with the aim of scrutinizing the distribution of adhesive in the bond line region. The distribution of thermal conductivity, as well as temperature in the bond line area, was measured on the surface by means of a nanofabricated thermal probe offering high spatial and thermal resolution. Both the thermal conductivity and the surface temperature measurements were found suitable to differentiate between materials in the bond region, i.e., adhesive, cell walls and embedding epoxy. Of the two SThM modes available, the surface temperature mode provided images with superior optical contrast. The results clearly demonstrate that the polyurethane adhesive did not cause changes of thermal properties in wood cell walls with adhesive contact. By contrast, cell walls adjacent to a phenol-resorcinol-formaldehyde adhesive showed distinctly changed thermal properties, which is attributed to the presence of adhesive in the wood cell wall.

Increasing the revenue from lignocellulosic biomass: Maximizing feedstock utilization

Replacing petroleum by biomass can be economically feasible by generating revenue from the three primary biomass constituents. The production of renewable chemicals and biofuels must be cost- and performance- competitive with petroleum-derived equivalents to be widely accepted by markets and society. We propose a biomass conversion strategy that maximizes the conversion of lignocellulosic biomass (up to 80% of the biomass to useful products) into high-value products that can be commercialized, providing the opportunity for successful translation to an economically viable commercial process. Our fractionation method preserves the value of all three primary components: (i) cellulose, which is converted into dissolving pulp for fibers and chemicals production; (ii) hemicellulose, which is converted into furfural (a building block chemical); and (iii) lignin, which is converted into carbon products (carbon foam, fibers, or battery anodes), together producing revenues of more than

Evaluation of the cure kinetics of the wood/pMDI bondline

500 per dry metric ton of biomass. Once de-risked, our technology can be extended to produce other renewable chemicals and biofuels.

Cradle-to-Gate Life-Cycle Inventory and Impact Assessment of Wood Fuel Pellet Manufacturing from Hardwood Flooring Residues in the Southeastern United States

Abstract Micro-dielectric analysis (μDEA) and differential scanning calorimetry (DSC) were used to monitor cure of polymeric diphenylmethane diisocyanate (pMDI) resin with wood strands in a saturated steam environment. A first-order autocatalyzed kinetic model was employed to determine kinetic parameters. The kinetics were found to follow an Arrhenius relation. A single ramp DSC technique and μDEA produced models that predicted similar results at higher cure temperatures, but the μDEA-based model predicts a longer cure time at low temperatures. The isothermal μDEA method yields higher activation energies and Arrhenius frequency factors than models based on single DSC ramps. A modification to ASTM E698 was made to conform to the assumption of autocatalyzed kinetics. The modified ASTM E698 method predicted an earlier end of cure than the μDEA-based models and was in agreement with DSC results obtained by partial cure experiments. The activation energies and frequency factors for the different cure monitoring methods are sensitive to different stages of cure.

A multivariate approach to the acetylated poplar wood samples by near infrared spectroscopy

Abstract In this article, we present cradle-to-gate life-cycle inventory (LCI) data for wood fuel pellets manufactured in the Southeast United States. We surveyed commercial pellet manufacturers in 2010, collecting annual production data for 2009. Weighted-average inputs to, and emissions from, the pelletization process were determined. The pellet making unit process was combined with existing LCI data from hardwood flooring residues production, and a life-cycle impact assessment was conducted using the Tool for the Reduction and Assessment of Chemical and Other Environmental Impacts (TRACI) model. The potential bioenergy and embodied nonrenewable energy in 907 kg (1 ton, the functional unit of this study) of wood fuel pellets was also calculated. The pelletization of wood requires significant amounts of electrical energy (145 kWh/Mg), but the net bioenergy balance is positive. Wood pellets require 5.8 GJ of fossil energy to produce 17.3 GJ of bioenergy (a net balance of 10.4 GJ/Mg). However, if environme...

Evaluating Cure of a pMDI-wood Bondline Using Spectroscopic, Calorimetric and Mechanical Methods

Abstract Yellow poplar (Liriodendron tulipifera L.) wood flour was chemically modified with acetic anhydride at varying times and initial moisture contents at a constant temperature. All samples exhibited increasing weight gains in the range of 5–16% with increasing reaction or treatment time. The acetylated poplar wood flour was characterized by means of Fourier transform infrared spectroscopy and near infrared (NIR) spectroscopy. Principal component analysis performed on the spectral data revealed clusters according to the esterification level. Partial least squares regression models developed from NIR data were able to predict the weight gain and the percentage of reacted OH groups. The correlations show that there is a direct and linear relationship between the spectra and the weight percentage gain and, therefore, the degree of acetylation.

Effects of organosolv fractionation time on thermal and chemical properties of lignins

Abstract The cure of polymeric diphenylmethane diisocyanate (pMDI)/wood bondline in a controlled saturated steam environment was monitored using micro-dielectric analysis (μDEA). Saturated steam environments were produced between 110°C and 140°C. The degree of cure calculated from μDEA was a basis for further spectroscopic, calorimetric, and mechanical evaluation. Interpretation of calorimetric and spectroscopic analysis revealed large consumption of isocyanate early in cure. However, mechanical strength, as revealed by lap-shear tests, did not develop until late in cure. Low lap-shear strengths and a plateau in conversion rates were detected for samples pressed at 110° and 120°C. Several components of the analysis suggest that low temperature cure may result in crystal formation, leading to diffusion controlled cure.

Improving Processing and Performance of Pure Lignin Carbon Fibers through Hardwood and Herbaceous Lignin Blends

Organosolv fractionation is a promising pathway to separate cellulosic biomass into high purity cellulose, hemicelluloses, and lignin. This work specifically investigates the properties of lignins isolated at specific time points as fractionation progressed, with the intent of correlating fractionation time with lignin purity, yield, thermal and chemical properties. Yellow poplar (Liriodendron tulipifera) was fractionated using a mixture of methyl isobutyl ketone, ethanol, and water with sulfuric acid as catalyst at 140 °C over a two-hour period. Aliquots of the liquor were collected by sampling every 15 min during the fractionation to generate a series of lignins. The results showed that with increased fractionation time, lignin purity improved from 90.3 to 94.6% and the glass transition temperature increased from 117 to 137 °C. The loss of aliphatic OH and increase of phenolic OH with fractionation time led to an increase in condensed structures and increased polydispersity at times greater than 90 min. Principal component analysis of Fourier transform infrared spectroscopic data confirmed the shift to higher purity and more condensed chemical structures with increasing fractionation time. Overall, this study demonstrates that thermal and chemical properties of lignin change with the organosolv fractionation time.

Chemical imaging of wood-polypropylene composites.

Lignin/lignin blends were used to improve fiber spinning, stabilization rates, and properties of lignin-based carbon fibers. Organosolv lignin from Alamo switchgrass (Panicum virgatum) and yellow poplar (Liriodendron tulipifera) were used as blends for making lignin-based carbon fibers. Different ratios of yellow poplar:switchgrass lignin blends were prepared (50:50, 75:25, and 85:15 w/w). Chemical composition and thermal properties of lignin samples were determined. Thermal properties of lignins were analyzed using thermogravimetric analysis and differential scanning calorimetry. Thermal analysis confirmed switchgrass and yellow poplar lignin form miscible blends, as a single glass transition was observed. Lignin fibers were produced via melt-spinning by twin-screw extrusion. Lignin fibers were thermostabilized at different rates and subsequently carbonized. Spinnability of switchgrass lignin markedly improved by blending with yellow poplar lignin. On the other hand, switchgrass lignin significantly improved thermostabilization performance of yellow poplar fibers, preventing fusion of fibers during fast stabilization and improving mechanical properties of fibers. These results suggest a route towards a 100% renewable carbon fiber with significant decrease in production time and improved mechanical performance.