Mark Driscoll - Academia.edu (original) (raw)
Papers by Mark Driscoll
Polymers, 2020
Ionizing radiation has become the most effective way to modify natural and synthetic polymers thr... more Ionizing radiation has become the most effective way to modify natural and synthetic polymers through crosslinking, degradation, and graft polymerization. This review will include an in-depth analysis of radiation chemistry mechanisms and the kinetics of the radiation-induced C-centered free radical, anion, and cation polymerization, and grafting. It also presents sections on radiation modifications of synthetic and natural polymers. For decades, low linear energy transfer (LLET) ionizing radiation, such as gamma rays, X-rays, and up to 10 MeV electron beams, has been the primary tool to produce many products through polymerization reactions. Photons and electrons interaction with polymers display various mechanisms. While the interactions of gamma ray and X-ray photons are mainly through the photoelectric effect, Compton scattering, and pair-production, the interactions of the high-energy electrons take place through coulombic interactions. Despite the type of radiation used on mat...
Radiation Physics and Chemistry, 2017
Nanocellulose is a high value material that has gained increasing attention because of its high s... more Nanocellulose is a high value material that has gained increasing attention because of its high strength, stiffness, unique photonic and piezoelectric properties, high stability and uniform structure. Through utilization of a biorefinery concept, nanocellulose can be produced in large volumes from wood at relatively low cost via ionizing radiation processing. Ionizing radiation causes significant break down of the polysaccharide and leads to the production of potentially useful gaseous products such as H 2 and CO. The application of radiation processing to the production of nanocellulose from woody and non-wood sources, such as field grasses, bio-refining byproducts, industrial pulp waste, and agricultural surplus materials remains an open field, ripe for innovation and application. Elucidating the mechanisms of the radiolytic decomposition of cellulose and the mass generation of nanocellulose by radiation processing is key to tapping into this source of nanocelluose for the growth of nanocellulostic-product development. More importantly, understanding the structural break-up of the cell walls as a function of radiation exposure is a key goal and only through careful, detailed characterization and dimensional metrology can this be achieved at the level of detail that is needed to further the growth of large scale radiation processing of plant materials. This work is resulting from strong collaborations between NIST and its academic partners who are pursuing the unique demonstration of applied ionizing radiation processing to plant materials as well as the development of manufacturing metrology for novel nanomaterials.
Energies, 2015
Lignin recovered from the hot-water extract of sugar maple (Acer saccharum) is used in this study... more Lignin recovered from the hot-water extract of sugar maple (Acer saccharum) is used in this study to synthesize adhesive blends to replace phenol-formaldehyde (PF) resin. Untreated lignin is characterized by lignin content and nuclear magnetic resonance (NMR) analysis. The molecular weight distribution of the lignin and the blends are characterized by size exclusion chromatography (SEC). The effect of pH (0.3, 0.65 and 1), ex situ furfural, and curing conditions on the tensile properties of adhesive reinforced glass fibers is determined and compared to the reinforcement level of commercially available PF resin. The adhesive blend prepared at pH = 0.65 with no added furfural exhibits the highest tensile properties and meets 90% of the PF tensile strength.
Radiation Physics and Chemistry, 2009
X-rays, derived from a high energy, high-current electron beam (EB), initiated in-situ polymeriza... more X-rays, derived from a high energy, high-current electron beam (EB), initiated in-situ polymerization of a unique class of monomers that were found to penetrate the cell walls of wood. X-rays initiated an auto-catalytic acrylic polymerization and penetrated through thick pieces of wood. The final cured product having the polymerizate, a polymer, both in the wood cell lumens and in the cell walls is called wood impregnated with a wood-polymer penetrant (WPP). The controlled lower dose rate of X-rays overcame disproportionation encountered when using higher dose-rate electron beam initiation. With X-rays, the in-situ polymerization took place in one exposure of modest dose. With EB, multiple passes were needed to avoid excessive heat build-up and monomer volatilization. Having entered the cell walls of the wood and then being polymerized within the cell walls, these radiation-cured unique monomers imparted outstanding dimensional stability upon exposure of the impregnated wood to humidity cycling. The preferred monomer system was also chemically modified prior to impregnation with agents that would remain in the wood and prevent the growth of fungi and other microbials. This technique differs from historic uses of monomers that merely filled the lumens of the wood (historic woodpolymer composites), which are only suitable for indoor use. The WPP impregnated wood that was either X-ray cured or EB cured demonstrated enhanced structural properties, dimensional stability, and decay resistance.
Radiation Physics and Chemistry, 2009
Carbon-fiber-reinforced composites were cured in molds using X-rays derived from a high-energy, h... more Carbon-fiber-reinforced composites were cured in molds using X-rays derived from a high-energy, high-current electron beam. X-rays could penetrate the mold walls as well as the fiber reinforcements and polymerize a matrix system. Matrix materials made from modified epoxy-acrylates were tailored to suitably low viscosity so that fiber wetting and adhesion could be attained. Techniques similar to vacuum-assisted resin transfer molding (VARTM) and conventional vacuum bagging of wet lay-ups were used. Inexpensive reinforced polyester molds were used to fabricate vehicle fenders. Moderately low-dose X-ray exposure was sufficient to attain functional properties, such as resistance to heat distortion at temperatures as high as 180 1C. The matrix system contained an impact additive which imparted toughness to the cured articles. ''Class A'' high gloss surfaces were achieved. Thermoanalytical techniques were used on small-sized samples of X-ray-cured matrix materials to facilitate selection of a system for use in making prototypes of vehicle components. X-rays-penetrated metal pieces that were placed within layers of carbon-fiber twill, which were cured and bonded into a structure that could be mechanically attached without concern over fracturing the composite. X-ray curing is a low temperature process that eliminates residual internal stresses which are imparted by conventional thermo-chemical curing processes.
Carbohydrate Polymers, 2014
Conversion of lignocellulosic biomass to value added products such as ethanol and other platform ... more Conversion of lignocellulosic biomass to value added products such as ethanol and other platform chemicals is enhanced by pretreatment, which reduces the crystallinity and molecular weight of cell wall polymers, thus increasing the available reaction sites. In this study, switchgrass (Panicum virgatum L) was pretreated with high energy electron beam (EB) irradiation to reduce its recalcitrance and achieve higher sugar conversion rates during treatment with cellulases and β-glucosidase. Conversion rates to sugars were compared before and after hot water (HW) extraction of EB-treated and control samples of switchgrass. Thermogravimetric analysis (TGA) was employed to determine peak degradation temperature of these EB-treated biomass samples before and after HW extraction, and near infrared spectroscopy (NIR) was used as a rapid technique to determine cellulose, hemicellulose, and lignin contents in the samples. TGA data confirms previously reported results that EB pretreatment reduces the molecular weight and crystallinity of cellulose and hemicellulose. This leaves hemicellulose more amenable to HW extraction and creates more cellulase-accessible sites, as shown by NIR and glucose yield data, respectively. Hemicellulose content was reduced from 30.2% to 16.9% after HW extraction and 1000 kGy EB treatment, and ultimate glucose yield after cellulase hydrolysis increased more than 4-fold. This study provides evidence that when EB pretreatment is utilized in combination with HW extraction, higher conversion rates and yields of glucose can be obtained from the cellulosic fraction of switchgrass.
Polymers, 2020
Ionizing radiation has become the most effective way to modify natural and synthetic polymers thr... more Ionizing radiation has become the most effective way to modify natural and synthetic polymers through crosslinking, degradation, and graft polymerization. This review will include an in-depth analysis of radiation chemistry mechanisms and the kinetics of the radiation-induced C-centered free radical, anion, and cation polymerization, and grafting. It also presents sections on radiation modifications of synthetic and natural polymers. For decades, low linear energy transfer (LLET) ionizing radiation, such as gamma rays, X-rays, and up to 10 MeV electron beams, has been the primary tool to produce many products through polymerization reactions. Photons and electrons interaction with polymers display various mechanisms. While the interactions of gamma ray and X-ray photons are mainly through the photoelectric effect, Compton scattering, and pair-production, the interactions of the high-energy electrons take place through coulombic interactions. Despite the type of radiation used on mat...
Radiation Physics and Chemistry, 2017
Nanocellulose is a high value material that has gained increasing attention because of its high s... more Nanocellulose is a high value material that has gained increasing attention because of its high strength, stiffness, unique photonic and piezoelectric properties, high stability and uniform structure. Through utilization of a biorefinery concept, nanocellulose can be produced in large volumes from wood at relatively low cost via ionizing radiation processing. Ionizing radiation causes significant break down of the polysaccharide and leads to the production of potentially useful gaseous products such as H 2 and CO. The application of radiation processing to the production of nanocellulose from woody and non-wood sources, such as field grasses, bio-refining byproducts, industrial pulp waste, and agricultural surplus materials remains an open field, ripe for innovation and application. Elucidating the mechanisms of the radiolytic decomposition of cellulose and the mass generation of nanocellulose by radiation processing is key to tapping into this source of nanocelluose for the growth of nanocellulostic-product development. More importantly, understanding the structural break-up of the cell walls as a function of radiation exposure is a key goal and only through careful, detailed characterization and dimensional metrology can this be achieved at the level of detail that is needed to further the growth of large scale radiation processing of plant materials. This work is resulting from strong collaborations between NIST and its academic partners who are pursuing the unique demonstration of applied ionizing radiation processing to plant materials as well as the development of manufacturing metrology for novel nanomaterials.
Energies, 2015
Lignin recovered from the hot-water extract of sugar maple (Acer saccharum) is used in this study... more Lignin recovered from the hot-water extract of sugar maple (Acer saccharum) is used in this study to synthesize adhesive blends to replace phenol-formaldehyde (PF) resin. Untreated lignin is characterized by lignin content and nuclear magnetic resonance (NMR) analysis. The molecular weight distribution of the lignin and the blends are characterized by size exclusion chromatography (SEC). The effect of pH (0.3, 0.65 and 1), ex situ furfural, and curing conditions on the tensile properties of adhesive reinforced glass fibers is determined and compared to the reinforcement level of commercially available PF resin. The adhesive blend prepared at pH = 0.65 with no added furfural exhibits the highest tensile properties and meets 90% of the PF tensile strength.
Radiation Physics and Chemistry, 2009
X-rays, derived from a high energy, high-current electron beam (EB), initiated in-situ polymeriza... more X-rays, derived from a high energy, high-current electron beam (EB), initiated in-situ polymerization of a unique class of monomers that were found to penetrate the cell walls of wood. X-rays initiated an auto-catalytic acrylic polymerization and penetrated through thick pieces of wood. The final cured product having the polymerizate, a polymer, both in the wood cell lumens and in the cell walls is called wood impregnated with a wood-polymer penetrant (WPP). The controlled lower dose rate of X-rays overcame disproportionation encountered when using higher dose-rate electron beam initiation. With X-rays, the in-situ polymerization took place in one exposure of modest dose. With EB, multiple passes were needed to avoid excessive heat build-up and monomer volatilization. Having entered the cell walls of the wood and then being polymerized within the cell walls, these radiation-cured unique monomers imparted outstanding dimensional stability upon exposure of the impregnated wood to humidity cycling. The preferred monomer system was also chemically modified prior to impregnation with agents that would remain in the wood and prevent the growth of fungi and other microbials. This technique differs from historic uses of monomers that merely filled the lumens of the wood (historic woodpolymer composites), which are only suitable for indoor use. The WPP impregnated wood that was either X-ray cured or EB cured demonstrated enhanced structural properties, dimensional stability, and decay resistance.
Radiation Physics and Chemistry, 2009
Carbon-fiber-reinforced composites were cured in molds using X-rays derived from a high-energy, h... more Carbon-fiber-reinforced composites were cured in molds using X-rays derived from a high-energy, high-current electron beam. X-rays could penetrate the mold walls as well as the fiber reinforcements and polymerize a matrix system. Matrix materials made from modified epoxy-acrylates were tailored to suitably low viscosity so that fiber wetting and adhesion could be attained. Techniques similar to vacuum-assisted resin transfer molding (VARTM) and conventional vacuum bagging of wet lay-ups were used. Inexpensive reinforced polyester molds were used to fabricate vehicle fenders. Moderately low-dose X-ray exposure was sufficient to attain functional properties, such as resistance to heat distortion at temperatures as high as 180 1C. The matrix system contained an impact additive which imparted toughness to the cured articles. ''Class A'' high gloss surfaces were achieved. Thermoanalytical techniques were used on small-sized samples of X-ray-cured matrix materials to facilitate selection of a system for use in making prototypes of vehicle components. X-rays-penetrated metal pieces that were placed within layers of carbon-fiber twill, which were cured and bonded into a structure that could be mechanically attached without concern over fracturing the composite. X-ray curing is a low temperature process that eliminates residual internal stresses which are imparted by conventional thermo-chemical curing processes.
Carbohydrate Polymers, 2014
Conversion of lignocellulosic biomass to value added products such as ethanol and other platform ... more Conversion of lignocellulosic biomass to value added products such as ethanol and other platform chemicals is enhanced by pretreatment, which reduces the crystallinity and molecular weight of cell wall polymers, thus increasing the available reaction sites. In this study, switchgrass (Panicum virgatum L) was pretreated with high energy electron beam (EB) irradiation to reduce its recalcitrance and achieve higher sugar conversion rates during treatment with cellulases and β-glucosidase. Conversion rates to sugars were compared before and after hot water (HW) extraction of EB-treated and control samples of switchgrass. Thermogravimetric analysis (TGA) was employed to determine peak degradation temperature of these EB-treated biomass samples before and after HW extraction, and near infrared spectroscopy (NIR) was used as a rapid technique to determine cellulose, hemicellulose, and lignin contents in the samples. TGA data confirms previously reported results that EB pretreatment reduces the molecular weight and crystallinity of cellulose and hemicellulose. This leaves hemicellulose more amenable to HW extraction and creates more cellulase-accessible sites, as shown by NIR and glucose yield data, respectively. Hemicellulose content was reduced from 30.2% to 16.9% after HW extraction and 1000 kGy EB treatment, and ultimate glucose yield after cellulase hydrolysis increased more than 4-fold. This study provides evidence that when EB pretreatment is utilized in combination with HW extraction, higher conversion rates and yields of glucose can be obtained from the cellulosic fraction of switchgrass.