Martin Hubbe

Abstract: With the inevitable coming of the Green Economy, biomass valorization, use of renewable and bio-based materials and development of high-performance, recyclable, biodegradable and biocompatible products are nowadays������������������ challenges and opportunities to welcome a more sustainable society. Yet, to hasten its arrival, we must answer the daunting question of how we transform these challenges to opportunities? By educating new generations of students to the multiplicity of opportunities or ����������������multiverse��������������� of biomass, from a scientific and engineering perspective to an entrepreneurial vision. The Department of Forest Biomaterials has decades of expertise in conversion and valorization of biomass into new fuels/energies and high-performance biomaterials that offer solutions to greenhouse gas emissions, environmental and aquatic pollution and waste accumulation.We propose to leverage our graduate curriculum by adding an entrepreneurial and business competency to its strong scientific and engineering core. Our envisioned integrated program aims at educating Master and PhD students from NC State University, and others (via an online version) by training them in the principles, practices and methodologies of biomass valorization, conversion, and usage.

The deposition of tacky substances, adhesives and non-polar soils is a serious problem in paper processing not only because it can cause an increase of defects in the finished products, but also it is responsible for a lower production rates, limited runnability, increased down time and equipment maintenance cost. Likewise, removal of fatty acids and unsaturated non-polar substances from fabrics is critical in view of the formulations used in detergency and cleaning and the need to reduce process water consumption. • Problems as those described before and associated with these different industrial processes are mainly due to non-polar, hydrophobic substances present in the aqueous systems (from fiber sources, soil and oily contaminant incorporated in process waters or during material handling). In the case of papermaking the nonpolar substances amount to 2-8% of the total composition based on solids but in the case of soiled fabrics this % composition can be even smaller. However, the effects of such small amounts of “contaminant” can be quite dramatic. • This project aims at substituting (partially or totally) current additives such as talc (papermaking) and detergents (fabrics and other surfaces) to eliminate deposits/non-polar soils. Therefore, we propose a new biotechnological method for deposit and soil control by using soybean meal, which contain lipoxygenase enzymes. Such system can block or remove deposits physically or biotechnologically via catalytic reactions involving the hydrolysis of triglycerides and unsaturated fatty acid, key components in deposit precursors. The lipoxygenases ability to degrade linoleic acid and related compounds has been demonstrated in our previous work and it is now proposed that they can be deployed in papermaking processes (and fabric as well as other surface treatment) by taking advantage of the breakdown of nonpolar substances that have adverse effects on product properties. Thus, in this period we will… • scale-up the discovered application and exploit industrially the capability of soybean meals to physically prevent deposit formation or to hydrolyze lipophilic compounds in process waters from different suspensions. • determine if the treatment has side benefits such as improved optical properties. This period will include pilot and industrial trials under different conditions and points of addition and also translation of the technology to commercial partners that have been identified.

In this project, we propose the use of soy-derived protein materials as the base for developing cost effective, advanced technology in papermaking. Papermaking and particularly paper recycling, depends heavily on materials to enhance both the processing and final product performance properties. These include: (a) Materials to provide optimization of water retention and drainage properties of the sheet during formation. This is critical to developing a low water, low energy paper process; (b) Additives to enhance the dry-strength of the fiber mat; (c) Products to provide surface modification and friction control/release in printing applications; (d) Maximize production rates for grades of paper based on recycled materials. Our preliminary observations are that the charged characteristics and size of soybean proteins is not unlike the polyampholytes we have been studying. Collaboration with an industrial partner and pilot paper machine trials are scheduled within this project. This will facilitate industrial deployment of our results, particularly in year 3 of our project. The applied activities will include the following: (a) We will evaluate degradation over time and final paper optical properties; (b) Based on our findings and in order to obtain desirable functional effects, we will fine tune the soybean protein streams by hydrolysis, combination with surfactants or other polymers, adjustment of pH and ionic strength of the medium, etc.; (c) In conjunction with Eka Chemicals, we will run specific pilot trial experiments to assess the protein influence on the papermaking properties of a recycled furnish; (d) We will then determine the best markets with Eka for its application while pursuing intellectual property; (e) We will engage GP in detailed conversations about its potential use in a mill trial (with the help of Eka Chemical).

The so-called pitch deposits from fiber raw materials continue to be an uncontrolled problem in most of the papermaking chemical and mechanical processes. We propose a 'green' route to combat such non-polar lipophilic extractives and deposits in papermaking by using soyprotein lipoxygenases. Central to the project is the conversion of triglcycerides, free and esterified sterols, resin acids, fatty alcohols and alkanes, all of which are responsible for pitch problems. The proposed solution is expected to improve paper machine runnability, paper friction and paper strength. The activity of lipoxygenase towards individual wood extractives and the role of transition metal ions in the further fragmentation of fatty acid hydroperoxides produced by lipoxygenase reaction will be elucidates and the collateral impact in reduction of lignin assessed.

We are proposing to utilize the natural amphoteric properties of soy derived proteins, to develop products that function to improve the water drainage from the wet paper mat and enhance the paper strength. These proteins would be based on crude protein or from waste streams associated with soy bean processing. Our preliminary observation is that the charged characteristics and size of these soybean proteins is not unlike the polyampholytes we have been studying. Collaboration with an industrial partner and pilot paper machine trials are scheduled within this project. This will facilitate industrial deployment of our results. The experimental activities, on the other hand, will include the following: (a) Characterization of protein materials: composition, Mw and size (multiangle light scattering), isolectric point (electrophoretic mobility); (b) Studies of the protein behavior in aqueous medium: degree of hydration, coupling with water, hydrodynamic ratio, rheological properties; (c) Application in paper-relevant applications: degree of adsorption, strength of binding, retention, drainage and dry strength. We will also will evaluate degradation over time and final paper optical properties; (d) Based on our findings and in order to obtain desirable functional effects, we will fine tune the soybean protein streams by hydrolysis, combination with surfactants or other polymers, adjustment of pH and ionic strength of the medium, etc.

The pulp & paper industry ranks in the top ten in US manufacturing having an annual output of nearly 80 billion dollars in sales. The industry is constantly looking for cost-effective methods for enhancing processing performance, final paper grade strength properties, printing performance, and surface modification/control (including paper production, recycled paper technology, enhanced container and packaging products, etc.). Interestingly, one of the largest uses of industrial grade proteins is for paper coatings, in which they serve as a pigment binder (www.andysmarket.com/ healthfacts/soyprotein.php). In this project we propose using soy-derived protein materials as the base for developing cost effective, advanced technology in this area. Papermaking and particularly paper recycling, depends heavily on materials to enhance both the processing and final product performance properties. These include: ? Materials to provide optimization of water retention and drainage properties of the sheet during formation. This is critical to developing a low water, low energy paper process. ? Additives to enhance the dry-strength of the fiber mat. ? Products to provide surface modification and friction control/release in printing applications. ? Maximizing production rates for grades of paper based on recycled materials.

A novel approach will be used to evaluate factors affecting the ability of probe chemicals to penetrate into porous media of differing void dimensions. The subject is of critical importance for drilling operations, cementation, and surfactant/ polymer-enhanced washing of drill cuttings, including situations where the penetration of complex fluids throughout constrained and tortuous pathways is aimed at displacing water or oil domains. Tests with selected cationic polyelectrolytes and surfactants will help us to understand factors that either favor or hinder complex fluid penetration. Whether or not a certain probe material is able to pass into pores of different size will be evaluated by a new assay in which the streaming potential of a suspension of polyelectrolyte-capped nanoporous particles is evaluated under strongly contrasting conditions of the ionic strength of an aqueous supporting electrolyte. By varying the molecular mass, branched structure, and charge density, and other properties of the probe molecules, research questions related to the reptation of macromolecules into spaces that restrict their thermodynamic degrees of freedom can be addressed. The generated knowledge will be useful in answering current challenges for the optimal formulation of environmentally responsible drilling fluids, surfactants in treatment of drill-cuttings (and soil) and enhanced oil recovery. The work also will help to understand the suppression of electrokinetic effects within very fine pores at low ionic strength. The project will contribute to the education of a graduate and two undergraduate students, as well as furthering a research program devoted to emerging applications of colloidal science.

This project is specifically designed to develop and enhance baccalaureate and Masters degree programs that will address all three USDA Priority Areas and multiple USDA Educational Need Areas, with its main focus on Priority Area #1 and Educational Need Areas 1 and 3. North Carolina State University (NCSU), North Carolina A&T (NCAT), and the University of Tennessee (UT) have identified mutual and complementary interests for the pursuit of an academic program in biomass for graduate (primarily) and undergraduate students. BIOSUCCEED: BIOproducts Sustainability, a University Cooperative Center for Excellence in Education is a regional center of excellence will be established from the successful implementation of this proposed effort. BIOSUCEED is closely aligned with ongoing efforts at NCSU, NCAT and UT. NCSU has started a campus-wide Forest Biomaterials & Biotechnology Initiative. NCAT has their interdisciplinary Energy and Environmental Studies graduate program and new undergraduate Clusters that cover Energy and the Environment, and Science and Technology. UT is taking a leadership role in the SUNGRANT program. BIOSUCEED?s innovation is based on the development of a complete MS degree program that can be delivered by any the three University partners, and via distance education means. BIOSUCCEED will develop six graduate (MS) level classes, two classes aimed at undergraduates, and individual lectures that can be included in individual classes. All of these classes will be offered at no cost to the national biomass community (essentially a free series of text books) and can be customized by any institution around the country. The partnering universities expect that BIOSUCCEED will produce students who will continue to spark the biomass revolution and produce renewable sources of materials, chemicals, and energy, and ultimately provide significant benefits in environmental compatibility and local economies.

The objectives of the Sustainability, Energy and Engineering (SEE) REU Site at North Carolina State University (NCSU) are threefold: (1) to develop future knowledge leaders in green engineering and sustainability, (2) to enhance the likelihood of successful graduate training in students from predominantly undergraduate institutions and from groups underrepresented in engineering, and (3) to develop in the participants disciplined thinking related to the ethical and economic motivations for implementation of sustainable practices. Sustainability requires consideration of a multitude of technical dimensions. SEE is therefore a multidisciplinary program, primarily grounded in Chemical Engineering, but including projects and researchers from Departments of Nuclear Engineering, Textile Engineering, Mechanical and Aerospace Engineering, Wood and Paper Science, Civil Engineering, and Chemistry. Twenty-one undergraduate students recruited from across the country will be engaged in this ten-week research and professional development program. Mentored by faculty and graduate students or post-docs, they will perform research on projects defined to help achieve environmental and energy sustainability through product or process engineering. Several of the projects will be sponsored in collaboration with two research centers that are nationally renowned for the development of environmentally benign solvents: the Kenan Center for the Utilization of Carbon Dioxide in Manufacturing (joint effort between the University of North Carolina at Chapel Hill and NCSU), and the NSF-supported Science and Technology Center (STC) for Environmentally Responsible Solvents and Processes. These research activities will culminate in a written report and presentation of a poster at a campus-wide research colloquium. Sustainability also encompasses economic, societal and ethical considerations. SEE students will attend the annual American Chemical Society Green Chemistry and Engineering Conference in Washington DC, where they will hear technical and business leaders discuss the status of green chemistry and engineering, opportunities for implementation of recently developed technologies, and details of success stories. We expect that this conference will convey to the students a sense of the global impact that their efforts can have, and that sustainability is an economically-viable global priority. SEE students will also participate in a day-long symposium entitled Ethics, Engineering, Energy and Environmental Sustainability, presented by nationally-renowned leaders in environmental ethics and in energy sustainability, and developed and organized by the North Carolina Solar Center and the STC. The primary objective of the symposium is to connect research and engineering practice with the ethical responsibilities of individuals and corporations for environmental stewardship.

Over the next three years, the project work to be carried out at North Carolina State University will focus on adhesion failure between paper and gypsum core. Emphasis will be placed on clarifying the mechanisms related to such failures and strategies for overcoming the problem.