Progress 02/15/17 to 02/14/21
Outputs
Target Audience:This research provided a new technology that makes epoxy bonded wood more water resistant and sustainable. Conventionally, the epoxy cannot be classified as a construction based adhesive due to its low moisture resistance during epoxy to wood bonding; however, bio-oil-epoxy bonded wood composites showed technological promise by performing well during water exposure. Additionally, it was discovered that bio-oil could be utilized for polymeric diphenylmethane diisocyanate (pMDI) adhesive systems for additional moisture resistance. Hybrid epoxy-pMDI-bio-oil mixtures also exhibited further promise for the manufacturer to dial in the desired wood composite moisture resistance. As such, industry manufacturers and adhesive suppliers were the main benefactors of this research. A key stakeholder in this research was Huber Corporation. The Director of Research from Huber was included on the graduate student committee. This allowed for an industry perspective in the students' research. To assist with this research, Huber donated thermal analytical equipment to help characterize the adhesive system. An industrial collaboration was beneficial because it ensured the research was in alignment with company/society needs. Huber was also invaluable in making sure the adhesive system would be practical as a drop in application within their oriented strand board plant and the wood composite industry in general. Forestry landowners was another key stakeholder for this research. In the southeastern United States, pulpwood has consistently been cheaper due to a large supply and high growth to harvest ratio. Ways to utilize pulpwood in the south will help to increase pulpwood prices for landowners. This research was beneficial because bio-oil from pulpwood was utilized in this research. Changes/Problems:One weakness to the project was that when the bio-oil epoxy resin was pressed under commercial time and pressures, the moisture resistance improved, but to that just below what isrequired by industry standards. We could achieveacceptable resultsby pressing longer, but this was not cost effective for industry. So we took this problem to our company partner (Huber) and they pointed out the flexibility and reactivity of pMDI. So to speed up the reaction and improve the moisture resistance, we followed the advice of our stakeholder and explored pMDI-epoxy mixtures with bio-oil. Small amounts of pMDI were found to accelerate thecure and improvemoisture resistance. One key limitationwas that the yield of bio-oil for lignin based streams was below 30% after optimization. This yield may still be too low to justify the economic usefor industrial applications, but we were able to double the yield by manipulating liquefaction conditions and using hydrothermalliquefaction. Ethanol extraction coupled with hydrothermal liquefaction further improved OH availability. Hydrothermal liquefaction was found to work better than pyrolysis and ethanol extraction was found to improve hydroxyl availability.To improve the yield, we also investigated mixing lignin with biomass to yield which increases the variability in available OH groups, but not to the degree of conventional bio-oil. Overall, we delivered all of the proposed objectives of the project and the modifications above where attempts to improve the system to reach industrystandards. What opportunities for training and professional development has the project provided?One graduate student developed a patent application for a self-curing bio-oil epoxidized resin. This path was due to his training which was a mixture of fundamental and industrial applications. Ultimately, he work was not patentable, but his professional development and training led him to work for a startup adhesives company which valued his mix of adhesive chemistry and industry culture. He has since been rehired by a corporation that makes adhesives for wood composites and other applications. Another graduate student was able to participate in mill trials. While the mill trials was not part of this project, inclusion of Huber into his committee for this project, led him to participate in a mill trial for another project. The mill trials was invaluable to the student because he was then able to leverage the industrial specifications and limitations to this project for practical application in the laboratory. He has now accepted a post doc position with the Forest Products Development Center at Auburn University to further his professional development as an industrial scientist. How have the results been disseminated to communities of interest?A key stakeholder in this research was Huber Corporation. The Director of Research from Huber was included on the graduate student committee. This allowed for an industry perspective in the students' research. This committee member provided input into his research and also participated in the final defense where he witnessed the products of this research. Huber was also invaluable in making sure the adhesive system would be practical as a drop in application within their oriented strand board plant and the wood composite industry in general. The work was also disseminated to many conferences. A key conference was the forest products society where we met many industry representatives. We also held annual meetings with the Forest Products Development Center Advisory Board. This board consists of 3 oriented strand board companies that make up the majority of volume produced in the U.S. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
Objective 1) develop ahydrothermal liquefied lignin (HTL)system coupled with a partial fractionation strategy that optimizes OH group number and distribution while minimizing energy input. In regular liquefied bio-oil, the hydroxyl groups in bio-oil were analyzed by a relatively new technique: quantitative 31P NMR. It was found that not only does the total hydroxyl number of bio-oil influence the yield and epoxy equivalent weight of bio-oil based epoxy resin, but also the distribution of hydroxyl groups within bio-oil (aliphatic, phenolic, and acidic OH) played an important role in the determination of the optimum amount of catalyst needed for synthesis. Similar results were found for hydrothermal liquefied lignin and has been submitted for publication. One key finding was that the yield of bio-oil for lignin based streams was below 30% after optimization. This yield may still be too low to justify the economic usefor industrial applications, but we were able to double the yield by manipulating liquefaction conditions and using hydrothermalliquefaction. We were also able to increase OH availability by 60% under these hydrothermal conditions. Low and high molecular weight compounds were fractionated successfully based on their vastly different densities causing them to easily separate into layers. Objective 2) modify the chemical functionalities of the bio-oil to formulate epoxy based resins with maximum crosslinking density for better structural properties. The distribution of aliphatic, acidic, and phenolic type OH groups were manipulated through hydrothermal liquefaction. It was found that aliphatic and acidic OH functionality increased with hydrothermal liquefaction while the total number of phenolics slightly decreased. Nevertheless, we were able to improve the compatibility between the phenolic component of bio-oil and epoxy resins. We also achievedmore than 10.8 mmol/g of total hydroxyl groups which makes this an alternative feedstock to replace phenols in epoxies. We were further able to use acetone extraction (1:7 mixing ratio) to elevate the cross linking density from 600 to 1900 mol/m^3. We hypothsize that the increased crosslink density helped to explain the heighted resistance to moisture. We also found that hydrothermal liquefaction worked better than pyrolysis. A water/ethanol mixture (1/1, wt/wt) was used as liquefying solvent in the HTL process at 300 ?C, and the pyrolysis bio-oil was produced at 450 °C. The effect of hydrothermal liquefaction on the physical and chemical properties of the bio-oils were characterized. The water/ethanol co-solvent used improved the bio-oil yield and reduced char yield relative to the conventional pyrolysis process. Objective 3+4) determine the additional bio-oil needed to improve the dimensional stability of the wood composite and to meet industry standards OSB was manufactured utilizing epoxy, and epoxy modifiedbio-oil as adhesive binder. The results showed that epoxy resin with a lignin based bio-oil content of 20% showed comparable bonding properties to that of polymeric diphenylmethane diisocyanate (PMDI). Bio-oil substitution of 20% improved the hydrophobicity of the OSB as well. The TGA and DSC analysis of the epoxy resins showed improved thermal stability at lower bio-oil substitution levels. It was concluded that epoxy resin amended bio-oil could be a potential adhesive to produce OSB. One weakness; however, is that when the bio-oil epoxy resin was pressed under commercial time and pressures, the moisture resistance improved but to that just below what isrequired by industry standards. We could achieveacceptable resultsby pressing longer, but this was not cost effective for industry. Future work should focus on further optimizing the crosslinking speed of the reaction. To speed up the reaction and improve the moisture resistance, we followed the advice of our stakeholder and explored pMDI-epoxy mixtures with bio-oil. Small amounts of pMDI were found to accelerate thecure and improvemoisture resistance.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2017
Citation:
Liu, Y., Via, B. K., Pan, Y., Cheng, Q., Guo, H., Auad, M. L., & Taylor, S. (2017). Preparation and characterization of epoxy resin cross-linked with high wood pyrolysis bio-oil substitution by acetone pretreatment. Polymers, 9(3), 106.
- Type:
Journal Articles
Status:
Submitted
Year Published:
2021
Citation:
Asafu-Adjaye, O. A., Street J., Peresin S. M., Adhikari, S., Auad, M. L., Liles T., Via, B. (2021). Oriented Strand Board Composites from Fast Pyrolysis Bio-oil-based Epoxy wood Adhesive. Submitted to Industrial Crops and Products.
- Type:
Journal Articles
Status:
Submitted
Year Published:
2021
Citation:
Asafu-Adjaye, O. A., Celikbag, Y., Street J., Peresin S. M., Adhikari, S., Auad, M. L., Via, B. (2021). Elucidation of the effect of Fast Pyrolysis and Hydrothermal Liquefaction on the Physico-chemical properties of Bio-oil from Loblolly Pine Biomass as Biopolyol. Submitted to Bioresource Technology
- Type:
Journal Articles
Status:
Submitted
Year Published:
2021
Citation:
Asafu-Adjaye, O. A., Rahman T. Street J., Bensode A., Peresin S., Adhikari, S., Auad, M. L., Via, B. (2021). Random Oriented Strand Board bonded with Hydrothermal Liquefaction Bio-oil-based Polymeric methane dipthenyl diisocyanate adhesive system. In preparation for International Journal of Adhesion and Adhesives
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
Vivek Patil and Sushil Adhikari. 2020. Capping the lignin to get plant-based chemicals: Stabilization of reactive groups during lignin fractionation for improving monomer yields. 2020 College of Agriculture Virtual Graduate Poster Showcase, Auburn University. October 29th, 2020.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
Vivek Patil, Sushil Adhikari, Hossein Jahromi. 2020. Phenolation as a pre-treatment to improve the reactivity of lignin in depolymerization reactions American Society of Agricultural and Biological Engineers (ASABE) Annual International Meeting. Oral presentation. July 12-15th, 2020. Virtual.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2021
Citation:
Vivek Patil and Sushil Adhikari. 2020. Plant-based renewable chemicals from lignin depolymerization with prior phenolation This is Research, Auburn University. March 29-April 2, 2020.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Asafu-Adjaye, O. and Via, B. 2019. Utilization & Characterization of Epoxy/Pyrolysis Bio-Oil Binder in Oriented Strandboard Production. 73rd International Convention Forest Products Society, Atlanta, Ga.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Asafu-Adjaye, O, Via, B. 2019. Characterization and Utilization of Epoxy/Pyrolysis Bio-Oil in Oriented Strand Board Production. Proceedings of the 62nd International Convention of Society of Wood Science and Technology October 20-25, 2019 Tenaya Lodge, Yosemite, California USA
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Vivek Patil and Sushil Adhikari. Waste no more: improving the selectivity of lignin depolymerization into phenolic monomers with phenol-redistribution mechanism. Graduate Student Poster Showcase, Auburn University College of Agriculture, Auburn, Alabama. October 23, 2019.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
New challenges in the polymer Industry: sustainable energy, medicine, water and food, Maria L. Auad, invited keynote speaker, Nanoscience in El Salvador, January 25-29, 2020.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2020
Citation:
Polymers for Advanced Applications: from controlled chemistry to unique properties, Maria L. Auad, the University of Alabama at Tuscaloosa, February 17-18, 2020.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Polymers for Advanced Applications: from controlled chemistry to unique properties, Maria L. Auad Nanofibers, Applications and Related Technologies Nart, Liberec, Czech Republic, September 18-20,2019.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2019
Citation:
Archana Bansode, Dr. Mehul Barde, Dr. Thomas Elder, Dr. Maria L. Auad, Characterization of kraft lignin for synthesis of bio-based phenol-formaldehyde resin as a wood adhesives, Graduate Engineering Research Showcase (GERS), Auburn, Alabama, 2019. (Poster)
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2017
Citation:
Novel thermoset polymeric networks from fast pyrolysis bio-oil. Barde M., Sibaja B., Celikbag Y., Via B., Adhikari S., Edmunds W., Labb� N., Auad M. L. 253rd American Chemical Society, San Francisco, CA; April 2-6, 2017. Oral Presentation.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2017
Citation:
High performance bio oil-based polymers and resins. Barde M., Auad M. L. Finish in 5, Auburn University, Auburn, AL; March 22nd, 2017. Oral Presentation.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2017
Citation:
Fast pyrolysis bio-oil as precursor of thermosetting resins. Barde M., Sibaja B., Auad M. L. 2016 AIChE Annual Meeting, San Francisco, CA, November 13-18, 2017. Poster Presentation.
- Type:
Conference Papers and Presentations
Status:
Other
Year Published:
2019
Citation:
Via, B. (2019). Development of sustainable adhesives, wood composites, and other biomaterials. West Virginia University, Morgantown, WV
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2017
Citation:
Celikbag, Y., Via, B.K. 2017. Self?curing Epoxy Resin as a Bio?based Adhesive for Wood Products. 2017 International Conference on Wood Adhesives. Atlanta, Ga.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2017
Citation:
Cheng, G., Via, B.K. 2017. Epoxy Resin Cross?linked with Wood Pyrolysis Bio?oil by Acetone Pretreatment for Wood Adhesion. 2017 International Conference on Wood Adhesives. Atlanta, Ga.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2017
Citation:
Celikbag, Y., Meadows, S., Barde, M., Adhikari, S., Buschle-Diller, G., Auad, M., Via, B.K. 2017. Synthesis and characterization of bio-oil-based self-curing epoxy resin. 253rd-American Chemical Society National Meeting Expo. San Francisco.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2017
Citation:
Celikbag, Y. Via, B.K., Adhikari, S., Auad, ML. 2017. Synthesis and Characterization of Bio?oil?based Self?curing Epoxy Resin. 71st FPS International Convention Program, Starkville, MS.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2017
Citation:
Celikbag, Y., Via, B.K., Adhikari, S., Auad, M., Buschle-Diller, G., Production of Biopolyol via Thermomechanical Conversion of Biomass: Hydrothermal Liquefaction vs. Organic Solvent Liquefaction. IBSS Conference, Oak Ridge, TN.
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Patil, V., Adhikari, S., Cross, P., & Jahromi, H. (2020). Progress in the solvent depolymerization of lignin. Renewable and Sustainable Energy Reviews, 133, 110359.
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Adhikari, S., Auad, M., Via, B., Shah, A., & Patil, V. (2020). Production of Novolac Resin after Partial Substitution of Phenol from Bio-Oil. Transactions of the ASABE, 63(4), 901-912.
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Patil, V., Adhikari, S., & Cross, P. (2018). Co-pyrolysis of lignin and plastics using red clay as catalyst in a micro-pyrolyzer. Bioresource technology, 270, 311-319.
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Barde, M., Celikbag, Y., Via, B., Adhikari, S., & Auad, M. L. (2018). Semi-interpenetrating novolac-epoxy thermoset polymer networks derived from plant biomass. Journal of Renewable Materials, 6(7), 724-736.
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Barde, M., Adhikari, S., Via, B. K., & Auad, M. L. (2018). Synthesis and characterization of epoxy resins from fast pyrolysis bio-oil. Green Materials, 6(2), 76-84.
- Type:
Journal Articles
Status:
Published
Year Published:
2020
Citation:
Celikbag, Y., Nuruddin, M., Biswas, M., Asafu-Adjaye, O., & Via, B. K. (2020). Bio-oil-based phenolformaldehyde resin: comparison of weight-and molar-based substitution of phenol with bio-oil. Journal of Adhesion Science and Technology, 34(24), 2743-2754.
- Type:
Journal Articles
Status:
Published
Year Published:
2017
Citation:
Celikbag, Y., Meadows, S., Barde, M., Adhikari, S., Buschle-Diller, G., Auad, M. L., & Via, B. K. (2017). Synthesis and characterization of bio-oil-based self-curing epoxy resin. Industrial & Engineering Chemistry Research, 56(33), 9389-9400.
- Type:
Journal Articles
Status:
Published
Year Published:
2017
Citation:
Hern�ndez, B. S., Barde, M., Via, B., & Auad, M. L. (2017). Sustainable products from bio-oils. Mrs Bulletin, 42(5), 365-370.
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Progress 02/15/18 to 02/14/19
Outputs
Target Audience:We reached out to a startup company (identity confidential) whom is interested in using bio-oilfor value added polymers. We also showed these results at the American Chemical Society to reach other chemists/scientistson the polymerization part. We also presented at the Forest Products Society International Conference whom has more industry stakeholders present. Changes/Problems:As mentioned previously, we were able to improve our bio-oilyield from 10 to 30% by switching from liquefaction to pyrolysis. Nevertheless, this is a still a low yield for industry adaptation. Ways to approach this are being explored. What opportunities for training and professional development has the project provided?Trained graduate students:Mehul Barde,OseiAsafu-Adjaye,Vivek Patil?. Post Doc - Charles Essien, George Cheng How have the results been disseminated to communities of interest?Reached out to wood composites manufacturer, Huber Corporation. Held Advisory Board meeting in Summer of 2018 to demonstrate progress. Taught some of the results in our new undergraduate curriculum Sustainable Biomaterials and Packaging. Also presented at Forest Products Society, ASABE, ACS, and SWST conference. Peer reviewed publications were also published. What do you plan to do during the next reporting period to accomplish the goals?Previously in 2017 there were issues liquefying ligninwith only a 10% yield. We were able to improve the yield to approximately 30% when using pyrolysis. We are still looking at solvents and other ligninstreams for better yields. We are also currently performing experiments looking at hydrophobic response of OSB with new system.
Impacts
What was accomplished under these goals?
Developed a recipe/methodology to cure epoxy-bio-oilsystem in wood composite using bio-oilas the catalyst. Developed practical ways to disperse in wood composite that can be used by industry. Developed a hydrophobic wood composite with bio-oilepoxy to replace tradition pMDIin the surface. Liquefaction and pyrolysisof kraftlignininto bio-oilwas achieved.
Publications
- Type:
Journal Articles
Status:
Awaiting Publication
Year Published:
2018
Citation:
Barde, M.; Celikbag, Y; Via, B., Adhikari, S.; Auad, M. L., Semi-interpenetrating novolac-epoxy thermoset polymer networks derived from plant biomass. Journal of Renewable Materials 2018. Manuscript accepted for publication.
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Barde, M.; Adhikari, S.; Via, B. K.; Auad, M. L., Synthesis and characterization of epoxy Resins from fast pyrolysis bio-oil. Green Materials 2018, 6 (2), 76-84.
- Type:
Journal Articles
Status:
Under Review
Year Published:
2018
Citation:
Barde, M.; Auad, M. L.; Jones, J.; Lu, N.; Pillay, S.; Ning, H., Natual fiber composite with ?-resorcylic acid based bio epoxy matrix. Manuscript submitted to Composites Part A: Applied Science and Manufacturing.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2018
Citation:
Asafu-Adjaye, O. Via, B.K., Adhikari, S., Auad, M. Bio-oil epoxy wood composites. 72nd Forest Products Society International Conference, Madison, WI; June 2018. Oral Presentation/Paper
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Sibaja, B., Adhikari, S., Celikbag, Y., Via, B., & Auad, M. L. (2018). Fast pyrolysis bio?oil as precursor of thermosetting epoxy resins. Polymer Engineering & Science, 58(8), 1296-1307.
- Type:
Other
Status:
Published
Year Published:
2018
Citation:
Asafu-Adjaye, O. Via, B.K., Adhikari, S., Auad, M.Assessment of the Effect of Fast Pyrolysis, and Hydrothermal Liquefaction Techniques on the Physico-Chemical Properties. 2018 Joint Convention Society Wood Science Technology, Japan. Fall 2019.
of Bio-oil from Loblolly Pine Biomass as Biopolyol
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Vivek Patil, Sushil Adhikari and Phillip Cross. 2018. Co-pyrolysis of lignin and plastics using red clay as catalyst in a micro-pyrolyzer. Bioresource Technology. Vol. 270, pp. 311-319.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2018
Citation:
2. Vivek Patil* and Sushil Adhikari. Role of in-situ hydrogen donor in lignin valorization for renewable fuels and chemicals. American Society of Agricultural and Biological Engineers (ASABE) annual meeting. Detroit, MI. July 30-Aug. 1, 2018.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2018
Citation:
Vivek Patil* and Sushil Adhikari. Using paper industry waste in a biorefinery. Auburn University Graduate Engineering Research Showcase. Auburn, AL. November 2017.
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