Source: WEST VIRGINIA UNIVERSITY submitted to NRP
EFFICIENT UTILIZATION OF BIOMASS FOR BIOPOLYMERS IN CENTRAL APPALACHIA
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
MCINTIRE-STENNIS
Reporting Frequency
Annual
Accession No.
0223687
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Oct 1, 2010
Project End Date
Sep 30, 2015
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
WEST VIRGINIA UNIVERSITY
886 CHESTNUT RIDGE RD RM 202
MORGANTOWN,WV 26505-2742
Performing Department
Forestry
Non Technical Summary
West Virginia is the third most heavily forested state in USA; produces 2.41 million dry tons of wood residues, and approximately 0.9 million dry tons of agricultural residues per year. A fraction of the wood residues are used as pellet fuel, boiler fuel, mulch and raw material for wood-composite products, while a portion of agricultural residues are used in biofuel production. Currently, there is a significant amount of biomass being underutilized that has great potential for valuable chemical production, particularly from the two common West Virginian hardwood species, northern red oak and yellow-poplar. Biomass for renewable energy, fuels, and chemicals has experienced a notable increase interest during the past few years. Particularly, biomass can be converted to valuable chemical products by fractioning and extracting its main components (cellulose, hemicellulose and lignin) via some of the following treatments or its combination: organic solvents, water, ionic liquids; energetic treatments, ultrasound, electrochemistry, etc. One example of high value materials from biomass (cellulose and/or hemicelluloses) are biofilms for the packaging and/or the pharmaceutical area. Lignin has also been used for biodegradable films in combination with starch, gelatin and/or cellulose; however, no specific application has been reported. Cellulose and hemicellulose biopolymers are hygroscopic in nature and films, as a result, do not behave well under conditions of high humidity. Previous research, largely aimed at overcoming such drawbacks, can be broadly broken down into categories based on the following approaches: 1) formation of composite films or films with additives and cellulose or hemicellulose as the major component, 2) coating of a hemicellulose film on a support layer, 3) chemical modification of the carbohydrates prior to film casting, 4) chemical modification of previously formed carbohydrate films. To date, no research has been performed to evaluate the effect of a fractioning process on the properties of the main biomass components with the aim to improve it for specific biofilm applications. This gap in research represents an opportunity need to be filled for future economic development at the West Virginia State. In the present work, the potential utilization of carbohydrate fractions and lignin from underutilized biomass for high values materials will give enormous development opportunities and impacts to the West Virginia State, which in future can be expanded to others states. The main impacts associated with the development of the proposed project are: social, since a reduction of residues from forest is expected; scientific and technical, since new developments and knowledge will be created; and economic, since it is expected to give high value to underutilized material.
Animal Health Component
(N/A)
Research Effort Categories
Basic
(N/A)
Applied
(N/A)
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
5110650202070%
5111599202030%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
0650 - Wood and wood products; 1599 - Grain crops, general/other;

Field Of Science
2020 - Engineering;
Goals / Objectives
The main goal of this research is to provide high value to underutilized renewable resources from central Appalachian hardwood and West Virginia agricultural residues, through its chemical conversion (fractionationg) in carbohydrates and lignin for biopolymers production. The specific objectives are: 1) To evaluate methodologies for fractionating carbohydrates (cellulose and hemicellulose) and lignin from underutilized woody and agricultural residues; 2) To evaluate methodologies to enhance separation and purification of extracted carbohydrates and lignin; 3) To study the acid-base properties of the fractionated and remaining material for further utilization; 4) To evaluate the feasibility of producing composite biofilms or coatings with additives and cellulose, hemicellulose and/or lignin as the major component. The expected outputs are: 1) A novel fractionation and extraction method for carbohydrate (cellulose and hemicellulose) and lignin separation from underutilized biomass; 2) Optimized method for carbohydrate and lignin separation and purification; 3) Biofilm or coating material based on the chemical fractions of underutilized biomass with enhanced properties for further utilization in the packaging or pharmaceutical area.
Project Methods
Logging residues from West Virginian hardwood species, northern red oak and yellow-poplar will be used as biomass source. Depending on the form (size and shape) of the wood residues the pretreatment will include a reduction of physical size of biomass and screening. After that, several treatments such as acetosolv process, hot water extraction and mild alkaline solutions will be evaluated at different concentrations and time of reaction. Finally, two methodologies will be evaluated for study and enhance the separation and purification of the extracted materials. These potentially will correspond to membrane and concentration (water removal)/centrifugation processes. The characterization of the fractionated material will include: Molecular weight: to determine the degree of polymerization of the products after the chemical conversion (fractioning) of the raw material; Lignin content: Acetosolv lignin or Soluble lignin by ultraviolet (UV); Sugar composition and acetyl groups by HPLC, uronic acids by UV; Acid-base properties of the lyophilized material using inverse gas chromatography (IGC); Thermal properties of the lyophilized material will be determined using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC); Mechanical properties of the lyophilized material will be determined using a dynamic mechanic analyzer (DMA). For obtaining the biofilm (biocomposite) or the coating material, and perform the correspondent characterization, the following methodology will be considered: The fractionated material plus some additives will be blended in a minicompounder and rheological properties will be determined. Accessories added on the minicompounder will allow the obtention of a biofilm. The properties of the final products will be evaluated with respect the conditions of the chemical conversion (fractioning). The characterization will include: Chemical analysis using infrared (IR) (or if possible Attenuated total reflectance infrared (IR-ATR); Wettability through the determination of receding and advancing angles using a contact angle analyzer and three different liquids (different acid-base properties), and acid-base properties using IGC. The final analysis will include determination of the surface energy, and subsequently the work of adhesion and the work of cohesion, for those bio-based composites. After the fractioning process, potential remaining material can be obtained. In this case, composites materials using traditional plastics (such as polyethylene or polypropylene) using a brabender mixer will be proposed to fabricate. The analysis of the potential remaining biomass and its composites will consist of: Lignin content (Klason lignin and acid soluble lignin); chemical composition (carbohydrate composition and acetyl groups by HPLC, uronic acids by UV); mechanical properties of composites will be determined using a DMA or an Instron universal test machine (UTM); acid-base properties of the reminded fibers will be determined using IGC, and finally the wettability of the composites will be evaluated through the determination of receding and advancing angles using a contact angle analyzer and three different liquids.

Progress 10/01/10 to 09/30/15

Outputs
Target Audience:During this period our target audience were academic and industry professionals working in the field of this report. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?The results of the research performed during 2015 have been partially disseminated through five publications (three peer reviewed articles and two conference papers, see above) and four conferences (oral & poster presentations). What do you plan to do during the next reporting period to accomplish the goals?This is a final report. No more plans for this research project.

Impacts
What was accomplished under these goals? Since this is a final report I would like to summarize the main outcomes of performing this research. Main product: A facile process to fabricate an hybrid material composed of cellulose and copper nanoparticles with antimicrobial properties feasible to be used in films for the food industry. Main outcomes: Six published peer-reviewed articles. Zhong T., Oporto G.S.*, Peng Y., Xie X., Gardner D.J. 2015. Drying cellulose-based materials containing copper nanoparticles. Cellulose DOI 10.1007/s10570-015-0646-7. Zhong T., Oporto G.S.*, Jaczynski J., Jiang Ch. 2015. Nanofibrillated cellulose and copper nanoparticles embedded in polyvinyl alcohol films for antimicrobial applications. Biomed Research International Article ID 456834. DeVallance D.B., Oporto G.S. and Quigley P. 2015. Investigation of hardwood (Red oak) biochar as replacement for wood flour in wood-polypropylene composites. Journal of Elastomers & Plastics DOI: 10.1177/0095244315589655. Moya R., Camacho D., Oporto G.S., Soto R., Mata J. and J. Valverde. 2014. Physical, mechanical and hydration kinetics of particleboards manufactured with woody biomass, agricultural wastes and tetra pak residues. Waste Management & Research 32(2) 106-114. Zhong T., Oporto G.S.*, Jaczynski J. Tesfai A. and J. Armstrong. 2013. Antimicrobial properties of the hybrid copper nanoparticles-carboxymethyl cellulose. Wood Fiber Sci. 45(2) 1-8. Oporto G.S.*, Kiziltas A., Gardner D.J., and D.J. Neivandt. 2011. Understanding the affinity between components of Wood-plastic composites from a surface energy perspective. J. Adhesion Sci. Technol. 25: 1785-1801. Eleven documents published in conference proceedings. Zhong T., Oporto G.S.*, Jaczynski J., Jiang Ch. 2015. Hybrid Cellulose-Copper Nanoparticles Embedded in Polyvinyl Alcohol for Antimicrobial Applications. In Proceedings of the 58th International Convention of Society of Wood Science and Technology, June 7-12, 2015, Jackson, Wyoming, USA. Zhong T., Oporto G.S.*, Peng Y. and Gardner D.J. 2015. Drying cellulose-based materials containing copper nanoparticles. 58th International Convention of Society of Wood Science and Technology, June 7-12, 2015, Jackson, Wyoming, USA. Oporto G.S., Zhong T., Jaczynski J. and R. Sabo. 2014. Microstructure, Mechanical, Thermal and Antimicrobial Properties of Hybrid Copper Nanoparticles and Cellulose Based Materials Embedded in Thermoplastic Resins. In Proceedings of the 57th International Convention of Society of Wood Science and Technology, June 23-27, 2014, Zvolen, Slovakia. Oporto G.S. Zhong T., Jaczynski J. and R. Sabo. 2013. Hybrid antimicrobial copper-cellulose based nanocomposite embedded in thermoplastic resins for active food packaging. 67th International Convention of the Forest Products Society, June 9-11, 2013, Austin, Texas, USA. Oporto G.S., Rodríguez S., Zhong T. and J. Jaczynski. 2013. Antimicrobial copper nanoparticles in cellulose-based materials for potential active food packaging applications. Tappi Place Flexible Packaging Symposium: New Technologies, April 8-10, 2013, Orlando Florida, USA. Oporto G.S., Rodríguez S., Zhong T. and R. Jara. 2012. Antimicrobial copper nanoparticles in cellulose based food packaging materials. Tappi International Conference on Nanotechnology for Renewable Materials. June 05-07, 2012, Montreal, Canada.. Oporto G.S., Rodríguez S., Zhong T. and R. Jara. 2012. Antimicrobial copper nanoparticles in cellulose based food packaging materials. 2012. Forest Product Society - 66th International Convention. June 03-05, 2012, Washington DC, USA. Oporto G.S., Jara R., Carrasco J. and D. DeVallance. 2012. Surface energy analysis on hot water extracted and torrefied Appalachian wood species for pellet production. Forest Product Society - 66th International Convention. June 03-05, 2012, Washington DC, USA. DeVallance D.B., Oporto G.S., Cheng Q. and P. Quigley. 2011. Thermal, mechanical, and physical properties of wood-plastic composites with added biochar. In Proceedings of the Forest Product society 65th International convention. June 19-21, Portland, OR, USA. Oporto G.S., 2011. Understanding the affinity between components of wood plastic composites from a surface energy perspective. In Proceedings of the Society of Plastic Engineers Annual Conference (ANTEC 2011). May 1-5, Boston, MA, USA. Oporto G.S. Gardner D.J., and R. Lopez-Anido. 2010. Interlaminar fracture mechanics applied to bonded wood plastic composites (WPCs) and hybrid WPC-fiber reinforced plastic composites. In Proceedings of the international SWST and United Nations economic commission for Europe, October 11-14, 2010, Geneva, Switzerland. Two peer reviewed manuscripts submitted in 2015 (in review) Zhong T., Oporto G.S.*, Jaczynski J., Jiang Ch. Cellulosic raw material to synthesize copper nanoparticles - Part 1: antimicrobial performance and state of oxidation of films. Submitted to Carbohydrate Polymers. Zhong T., Oporto G.S.*, Jaczynski J., Jiang Ch. Cellulosic raw material to synthesize copper nanoparticles - Part 2: copper release, thermal and mechanical properties of their films. Submitted to Carbohydrate Polymers. One Book Chapter in Press Gardner D.J., Oporto G.S. and W. Tze. 2015. Wood and fiber-based composites: surface properties and adhesion. In: Lignocellulosic fibers and wood handbook. (Ed. Antonio Pizzi and Mohamed Belgacem; Scrivener Publishing LLC). Pp 78. One Book Chapter in Review Zhong T., Oporto G.S. and J. Jaczynski. Cellulose-Copper Nanoparticles Embedded in Thermoplastic Resins for Antimicrobial Packaging Applications. In: Nanotechnology in Food Industry (ELSEVIER) One Book Chapter in Preparation Peng Y., Oporto G.S.,*, Zhong T. and D.J. Gardner. Drying Cellulose Nanomaterials: a Latent Challenge. In: Applications of NanoBioMaterials (I-XI) Multi-Volume SET Additionally, the research performed generated data for the submission of five new proposals, two of them funded. 5 Proposals submitted

Publications

  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Jiang Ch., Oporto G.S.*, Zhong T. Jaczynski J. 2015. TEMPO nanofibrillated cellulose as template for controlled release of antimicrobial copper from PVA films. Cellulose. DOI: 10.1007/s10570-015-0834-5.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Zhong T., Oporto G.S.*, Peng Y., Xie X., Gardner D.J. 2015. Drying cellulose-based materials containing copper nanoparticles. Cellulose DOI 10.1007/s10570-015-0646-7.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: Zhong T., Oporto G.S.*, Jaczynski J., Jiang Ch. 2015. Nanofibrillated cellulose and copper nanoparticles embedded in polyvinyl alcohol films for antimicrobial applications. Biomed Research International Article ID 456834.
  • Type: Journal Articles Status: Published Year Published: 2015 Citation: DeVallance D.B.*, Oporto G.S. and Quigley P. 2015. Investigation of hardwood biochar as replacement for wood flour in wood-polypropylene composites. Journal of Elastomers & Plastics DOI: 10.1177/0095244315589655.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Zhong T., Oporto G.S., Jaczynski J., Jiang Ch. 2015. Hybrid Cellulose-Copper Nanoparticles Embedded in Polyvinyl Alcohol for Antimicrobial Applications. In Proceedings of the 58th International Convention of Society of Wood Science and Technology, June 7-12, 2015, Jackson, Wyoming, USA.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Oral Presentation Oporto, Gloria. Drying cellulose-based materials containing copper nanoparticles. 58th International Convention of the Society of Wood Science and Technology. Jackson, Wyoming, USA. June 7-12, 2015
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Zhong, Tuhua. Hybrid Cellulose-Copper Nanoparticles Embedded in Polyvinyl Alcohol for Antimicrobial Applications. 58th International Convention of the Society of Wood Science and Technology. Jackson, Wyoming, USA. June 7-12, 2015.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Zhong, Tuhua. Antimicrobial performance of polyvinyl alcohol films embedded with hybrid cellulose-copper nanoparticles. WVU-Nineteen Annual Davis College Graduate Student Research Competition. Evansdale Library, Morgantown, WV, USA. April 7, 2015
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Zhong, Tuhua. Hybrid Cellulose-Copper Nanoparticles Embedded in Polyvinyl Alcohol Films for Antimicrobial Applications. 58th International Convention of the Society of Wood Science and Technology. Jackson, Wyoming, USA. June 7-12, 2015.


Progress 10/01/13 to 09/30/14

Outputs
Target Audience: During this period our target audience were not only academic professionals working in the area of lignocellulosic materials, but also from industry. We established contact with Renmatix (www.renmatix.com) and started performing general services to them. During 2015 we will be writing a research proposal together with Renmatix that considers the use of their lignins as template to attach copper nanoparticles and its further application as antimicrobial fillers for thermoplastic resins. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest? The results have been disseminated through the participation in the conferences mentioned in events (international and locally). What do you plan to do during the next reporting period to accomplish the goals? During 2015 we will be writing a research proposal together with Renmatix that considers the use of their lignins as template to attach copper nanoparticles and its further application as antimicrobial fillers for thermoplastic resins.

Impacts
What was accomplished under these goals? The most important result accomplished during this period was the development of methodology to dry the hybrid nanocellulose-copper nanoparticles.

Publications

  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Carrasco J.C., Oporto G.S.*, Zondlo J. and J. Wang. 2014. Observed Kinetic Parameters during the Torrefaction of Red Oak (Quercus rubra) in a Pilot Rotary Kiln Reactor. Bioresources 9(3) 5417-5437.
  • Type: Journal Articles Status: Published Year Published: 2014 Citation: Moya R., Camacho D., Oporto G.S., Soto R., Mata J. and J. Valverde. 2014. Physical, mechanical and hydration kinetics of particleboards manufactured with woody biomass (Cupressus lusitanica, Gmelina arborea,Tectona grandis), agricultural wastes and tetra pak residues. Waste Management & Research 32(2) 106-114. (PUBLISHED)
  • Type: Journal Articles Status: Under Review Year Published: 2014 Citation: Zhong T., Oporto G.S., Peng Y., Xie X. and D. Gardner. Drying cellulose-based materials containing copper nanoparticles. (Submitted to: Cellulose Journal).
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Participation in the 2014 International Convention. Society of Wood Science and Technology, Zvolen, Slovakia, June 23-27. Oral presentation. Title: Microstructure, mechanical, thermal and antimicrobial properties of hybrid copper nanoparticles and cellulose based materials embedded in thermoplastic resins.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2014 Citation: Participation at the 2014 WVU-Eighteen Annual Davis College Graduate Student Competition. Towers Gold and Blue Room, Morgantown, WV. April 9. Poster presentation by Zhong T. and Oporto G.S. Title: Effect of Freeze and Spray Drying Processes on the Morphology and Particle Size Distribution of the Hybrid Cellulose-Copper Nanoparticles.


Progress 01/01/13 to 09/30/13

Outputs
Target Audience: During this period our target audience were academic professionals working in the field of this report. We also were seeking funds to support the continuation of our research. During 2013 we established a Joint Venture Agreement between WVU (Forestry) and the USDA Forest Service Forest Product Laboratory in Madison Wisconsin. The main goal of this agreement is to develop preliminary experiments in the field of nanocomposites for packaging applications. Dr. Ronald Sabo, a Research Materials Engineer, is our main contact in Madison, WI. Changes/Problems: During 2014 our main research focus will be on Project 1 : Synthesis of copper nanoparticles on cellulose-based materials for potential packaging field application. What opportunities for training and professional development has the project provided? During 2013 my student and I had the opportunity to work at the USDA Forest Service Forest Product Laboratory in Madison Wisconsin. We both were producing composites using the material we prepared in our laboratories here at WVU. How have the results been disseminated to communities of interest? The results of the research performed during this year have been partially disseminated through two publications and two conferences (oral & poster presentations). We are preparing a manuscript which will be submitting for publication during the first months of 2014. What do you plan to do during the next reporting period to accomplish the goals? To work closely with the USDA Forest product laboratory and the company PPG Industries (Industrial coatings) to advance in the development of our product: “Hybrid cellulose nanocomposite for packaging applications”.

Impacts
What was accomplished under these goals? Based on the main goal of my McStennis project: Finding alternatives to valorize underutilized renewable resources from central Appalachian hardwood, the following outputs were reached in the following two areas in development: High value products from renewable wood-based materials: Project 1 - Graduate student 1: Synthesis of copper nanoparticles on cellulose-based materials for potential packaging field application. Main result for this period: Preliminary fabrication of a film nanocomposite using the hybrid cellulose-copper nanoparticles already developed and thermoplastic resins (polypropylene and polylactic acid). Main output during the reported period: Copper nanoparticles were synthesized “in situ” on carboxymethyl cellulose (CMC) and preliminary onto 2, 2, 6, 6-tetramethyliperidine-1-oxyl radical-oxidized (TEMPO-oxidized) cellulose nanofibers (CNFs). Both hybrid materials were initially embedded in thermoplastic resins consisted of polypropylene (PP) and polylactic acid (PLA). Using equipment available at the Forest Product Laboratory in Madison Wisconsin, preliminary composites were prepared using a twin-screw extruder followed by both injection molding process and a dry film formation process. Morphological and copper elemental mapping analyses on the hybrids cellulose-copper nanoparticles and on the extruded-injected composites were performed using scanning electron microscopy-energy dispersive X-ray microscopy (SEM-EDX). Thermal and mechanical properties of the extruded-injected composites were analyzed using differential scanning calorimetry (DSC) and through a tensile test (ASTM D638), respectively. The morphological analysis of those composites revealed that some of the hybrid material were well distributed on the thermoplastic resins, however a large amount of the hybrid material remained as aggregates. The tensile strengths of PP and PLA composites decreased in average up to 19.2% after the incorporation of the hybrid copper nanoparticles-cellulose based material. Thermal analysis showed no distinctive changes in the glass transition temperature and melting temperature for both PP and PLA composites after the incorporation of the hybrid material. An increase in the crystallinity of PP and PLA composites compared to the pure thermoplastic resins was observed. The concentration of copper ions released from the hybrid copper nanoparticles and cellulose based materials embedded in thermoplastic resins was determined using Atomic Absorption Spectrometry (AAS). The preliminary results showed that even though copper ions are migrating from the surface of films, the rate of this migration is too slow that is not affecting the antimicrobial properties of the films against E.coli DH5. No migration of copper ions was found for those extruded-injected composites. The preliminary results were used to prepare a research proposal which was submitted to the USDA-NIFA. This proposal was funded and those funds will complement the research being performed with my McIntire Stennis funds. Pre-treatment of red oak (Quercus rubra) and yellow poplar (Liriodendron tulipifera L.) for enhanced biofuel properties: Project 2 - Graduate student 2: Torrefaction Kinetics of Red Oak (Quercus rubra) in a Fluidized Reactor. Main result for this period: Determination of the kinetic parameters of torrefied red oak. That is, information regarding the behavior of wood in terms of its properties as a biofuel, when temperature and time are changing during the torrefaction process. Main output during the reported period: Different kinetic models have been proposed to characterize torrefaction of biomass, demonstrating dependencies on the raw material, experimental system, reaction time, and temperature. Conventionally, stationary processes have been used for kinetics studies of the torrefaction process. In this research, the torrefaction of red oak (Quercus rubra) in a bench-scale fluidized reactor was studied with emphasis on determining the kinetic parameters and improving the final material energy density. Mass loss and ultimate, proximate, and gross calorific analyses were performed on the resulting torrefied material. The primary reaction variables were the temperature (230 °C, 270 °C, 300 °C, and 330 °C) and the residence time (10 min, 20 min, and 30 min). The effect of temperature on the mass loss and energy density was much more significant than that produced by the increase in residence time. For the conditions studied, a one-step kinetic model with a first-order reaction proved adequate to describe the torrefaction of red oak in the fluidized reactor. The reaction rate constant (k) for the torrefaction reaction was found to be 0.212 min-1 at 300 °C. The activation energy and frequency factor were 11.9 kJ/mol and 2.57 min-1, respectively. Project 3: Co-firing torrefied material with coal. We stopped this research area since my main grad student left the program.

Publications

  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Zhong, Tuhua. 2013. Microstucture, mechanical, thermal and antimicrobial properties of hybrid copper nanoparticles and cellulose based materials embedded in thermoplastic resins. Austin, TX.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Zhong T., Oporto G.S., Jaczynski J. Tesfai A. and J. Armstrong. 2013. Antimicrobial properties of the hybrid copper nanoparticles-carboxymethyl cellulose. Wood Fiber Sci. 45(2) 1-8.
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Carrasco J.C., Oporto G.S., Zondlo J. and J. Wang. 2013. Torrefaction kinetics of red oak (Quercus rubra) in a fluidized reactor. Bioresources 8(4) 5067-5082.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Oporto, Gloria. Hybrid antimicrobial copper-cellulose based nanocomposite embedded in thermoplastic resins for active food packaging. 2013. Tappi Place Flexible Packaging Symposium: New Technologies. Orlando, FL.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Carrasco, Juan. 2013. Torrefied woody biomass with coal: A new challenge for power generation and wood pellets. WVU-Seventeenth Annual Davis College Graduate Student Competition. Morgantown, WV.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2013 Citation: Oporto, Gloria. 2013. Hybrid antimicrobial copper-cellulose based nanocomposite embedded in thermoplastic resins for active food packaging. 67th Forest Product Society & 56th SWST International Convention. Austin, TX.


Progress 01/01/12 to 12/31/12

Outputs
OUTPUTS: Based on the main goal of my McStennis project: Finding alternatives to valorize underutilized renewable resources from central Appalachian hardwood, the outputs are given on the following two areas in development: a)High value products from renewable wood-based materials: Project 1 - Graduate student 1: Synthesis of copper nanoparticles on cellulose-based materials for potential packaging field application. A simple method to produce a cellulose base material with antimicrobial properties was developed by introducing copper nanoparticles on carboxymethyl cellulose (CMC) using sodium borohydride as a copper reducing agent. The hybrid material was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM). SEM and EDX analysis confirmed the formation of copper nanoparticles within the carboxymethyl cellulose matrix. Transmission electron microscopy indicated that copper nanoparticles diameter was 10-20 nm. The antimicrobial properties of the hybrid material were effectively evaluated against the non-pathogenic surrogate of foodborne pathogen Escherichia coli. b)Pre-treatment of red oak (Quercus rubra) and yellow poplar (Liriodendron tulipifera L.) for enhanced biofuel properties: Project 2 - Graduate student 2: Torrefaction and pelletizing processes of red oak and yellow poplar before and after a hot water extraction process. In this research we study the combination of torrefaction and densification processes of underutilized renewable biomass composed by red oak (Quercus rubra) and yellow-poplar (Liriodendron tulipifera L.) for improving their further utilization in thermochemical conversion processes. Torrefaction process was performed at a laboratory scale using a fluidized reactor. The temperature in varied between 250*C and 300*C and reaction times were between 15 min to 30 min. The characterization of the torrefied material included thermogravimetric, proximate and ultimate analysis, calorific value, surface area, scanning electron microscopy, and surface energy (dispersion and acid base component). Pelletizing process was performed at a laboratory scale using a fixed temperature and time; lateral compression test were performed on the fabricated pellets. Both species, red oak and yellow poplar, resulted appropriate for torrefaction processes giving calorific values ranging from 4183 kcal kg-1 for the untreated material, up to 6218 kcal kg-1 for the torrefied material. Both species were also appropriated to pelletize them; however, high pressure and temperature were required. Project 3: Co-firing torrefied material with coal. Co-firing experiments using torrefied material in combination with coal were performed using thermogravimetric analysis coupled to Fourier transform infrared spectroscopy (TGA/FTIR). They showed promising results such as similar coal combustion behavior but less CO2 emissions. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Based on the main goal of my McStennis project: Finding alternatives to valorize underutilized renewable resources from central Appalachian hardwood, the outcomes are given on the following two areas in development: a)High value products from renewable wood-based materials: Project 1 - Graduate student 1: Synthesis of copper nanoparticles on cellulose-based materials for potential packaging field application. Main outcomes - impacts: -Different sequences of washing were introduced in the process of synthesis of copper nanoparticles in carboxymethyl cellulose. -A methodology to analyze the antimicrobial properties of the hybrid copper nanoparticles - cellulose based material was developed. Effective antimicrobial activity against the non-pathogenic surrogate of foodborne pathogen Escherichia coli was demonstrated. b)Pre-treatment of red oak (Quercus rubra) and yellow poplar (Liriodendron tulipifera L.)for enhanced biofuel properties: Project 2 - Graduate student 2: Torrefaction and pelletizing processes of red oak and yellow poplar before and after a hot water extraction process. Project 3 - Graduate student 2: Co-firing torrefied material with coal. Main outcomes - impacts: -Laboratory torrefaction and pelletizing set-up implemented. -Effective combination of torrefaction and densification processes of underutilized renewable biomass composed by red oak (Quercus rubra) and yellow-poplar (Liriodendron tulipifera L.) for improving their further utilization in thermochemical conversion processes. -Preliminary and successful experiments on co-firing torrefied wood and coal.

Publications

  • No publications reported this period


Progress 01/01/11 to 12/31/11

Outputs
OUTPUTS: The results obtained during the period covered in this report will be disseminated through the redaction of papers to be submitted in refereed journals and in the participation of conferences during 2012. These conferences will be in the area of nanotechnology and bioenergy. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
During this period the following two research approaches were performed with the final long term goal to obtain high value products from wood. -Hot water extraction using yellow poplar and red oak. Yellow poplar and Red oak wood chips were extracted using hot water in an agitated batch system using a Parr reactor (model 4843). The extractions were performed for a range of 150-170C and 45-90 minutes with a liquid/wood ratio (L/W) of approximately 7. The extracted wood was oven dried overnight at 103C and its weight determined. The extraction yield was calculated by comparing the amount of oven dry wood in the extraction cell before and after water extraction. The extraction yield for red oak at 170C and 90min was 30.3 percent and the extraction yield for yellow poplar at the same conditions was 24.2 percent. Sugar determination The total carbohydrate monomeric content on liquid samples was determined by High Performance Liquid Chromatography with Refractive Index Detection analysis. Samples and standards where place in autoclave at 121C for one hour. Sorbitol was used as internal standard. The results of sugar determination indicate that for red oak the high amount of hemicelluloses (especially Xylose) removed form wood occurs at 160C and 90 min. For yellow poplar the higher content of hemicelluloses occurs at 170C and 90 min. Lignin determination Acid insoluble lignin (Klason lignin) content was determined in the original and extracted wood according to Effland (1977). For red oak the Klason lignin in the original material was 17.6 (percent of wood). After the extraction at 170C and 90 min the lignin content increased to 28.2 (percent of wood). For yellow poplar the Klason lignin in the original material was 21.2 (percent of wood) and after the extraction at 170C and 90 min the content increased to 29.7 (percent of wood). The remaining solid material (obtained after the extractions) was characterized as well in terms of their surface area and surface energy and their feasibility to be used for pellet energy applications. 2.Use of cellulose nanostructure as template and stabilizer for metal nanoparticles with emphasis of application as antimicrobial nanocomposites for packaging. During this period our research was focused on to utilize carboxymethyl cellulose as a template for the synthesis of nanostructures. Cu2+-carboxymethyl cellulose chelate was obtained via an in situ approach. After removing excess cupric ions by dialyzing Cu2+-carboxymethyl cellulose chelate solution, copper nanoparticles were grafted on the surface of carboxymethyl cellulose through the addition of the reducing agent sodium borohydride. Scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) analyses confirmed the formation of copper nanoparticles on the surface of carboxymethyl cellulose. Our further investigation consists in to establish the basis for environmentally friendly cellulose-based food packaging containing copper nanoparticles with promising biocidal activities against spoilage and pathogenic microorganisms, and to establish well strategies for controlled release of antimicrobial agent from food packaging.

Publications

  • No publications reported this period


Progress 01/01/10 to 12/31/10

Outputs
OUTPUTS: During this period of time the investigator has participated in the SWST (Society of Wood Science & Technology) international conference performed in Geneva, Switzerland (October 11 to 14th) in which some of the topics presented were closely related to the topic of this project. Interesting contacts were made with potential collaborators in Hungary and Chile. A detailed description of the analyses that will be performed on the raw material (underutilized wood residues) has been prepared and is expected to start with the analyses next month (February 2011). PARTICIPANTS: A graduate student is expected to join the main investigator in performing this research. This study will be performed within the Division of Forestry and Natural Resources of West Virginia University (WVU). Collaboration with the Chemical Engineering, Mineral Resources and the Chemistry departments is expected. Special collaboration will be established with the Unidad de Desarrollo Tecnologico of the University of Concepcion in Chile and potential future developments will be faced altogether. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
No findings or results yet.

Publications

  • No publications reported this period