15 Sep 2023

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Nature volume 621pages 306–311 (2023)
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Nearly all adhesives1,2 are derived from petroleum, create permanent bonds3, frustrate materials separation for recycling4,5 and prevent degradation in landfills. When trying to shift from petroleum feedstocks to a sustainable materials ecosystem, available options suffer from low performance, high cost or lack of availability at the required scales. Here we present a sustainably sourced adhesive system, made from epoxidized soy oil, malic acid and tannic acid, with performance comparable to that of current industrial products. Joints can be cured under conditions ranging from use of a hair dryer for 5 min to an oven at 180 °C for 24 h. Adhesion between metal substrates up to around 18 MPa is achieved, and, in the best cases, performance exceeds that of a classic epoxy, the strongest modern adhesive. All components are biomass derived, low cost and already available in large quantities. Manufacturing at scale can be a simple matter of mixing and heating, suggesting that this new adhesive may contribute towards the sustainable bonding of materials.
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Data generated during the current study are available from the corresponding author on request.
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We thank P. Zavattieri and F. B. Rodriguez from the Lyles School of Civil Engineering at Purdue University for use of their MTS Insight instrument for adhesion testing. Help with microscopy by M. Meger, R. Seiler and C. Gilpin at the Purdue Life Science Microscopy Facility is appreciated. H. Siebert contributed to the initial experiments for this project. This work was supported by Office of Naval Research grant nos. N00014-19-1-2342 and N00014-22-1-2408.
These authors contributed equally: Clayton R. Westerman, Bradley C. McGill
Department of Chemistry, Purdue University, West Lafayette, IN, USA
Clayton R. Westerman, Bradley C. McGill & Jonathan J. Wilker
School of Materials Engineering, Purdue University, Neil Armstrong Hall of Engineering, West Lafayette, IN, USA
Jonathan J. Wilker
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C.R.W. and B.C.M. performed experiments. J.J.W. oversaw the project. The paper was written by all of the authors.
Correspondence to Jonathan J. Wilker.
The authors declare no competing interests.
Nature thanks the anonymous reviewers for their contribution to the peer review of this work. Peer reviewer reports are available.
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a, Representation of reactivity in a classic epoxy adhesive. Amine nucleophiles react with the three-membered epoxy rings to form covalent cross-links. The cross-linked product here is a depiction of a more extensive matrix. b, Nucleophiles and phenolics that were reacted with epoxidized soy oil to generate several adhesives formulations. In each case, there was one nucleophile, one phenolic, and epoxidized soy oil. The structures shown for lignin and tannic acid are approximate.
Two wood substrates are bonded together with an adhesive and then placed into the materials testing system. Each substrate has pin holes at the ends. One pin holds the bottom substrate in place. The top pin is attached to the moving crosshead and goes through the upper substrate. As the crosshead moves up and force is applied, a load cell measures force. The recorded force at joint failure is then divided by the substrate overlap area (1.2 x 1.2 cm here) to generate adhesion values in MPa.
a, Adhesion as a function of varied ratios between the components epoxidized soy oil, glycerol, and tannic acid. The substrates were untreated aluminum and curing was at 180 °C for 24 h. b, Adhesion as a function of varied ratios between the components epoxidized soy oil, malic acid, and tannic acid. The substrates were untreated aluminum and curing was at 180 °C for 24 h. c, Adhesion of soy-mal-tan over time when cured at 180 °C and with polished steel substrates. d, Adhesion of soy-mal-tan with changes to substrates and cure conditions. All error bars in panels ac are 90% confidence intervals averaged from n = 5 samples with the exception of n = 10 samples for the 24 hour time point in panel c. The ± values in panel d are 90% confidence intervals from an average of n = 5 samples for the 6 hour, 180 °C cure. All other data are from n = 10 samples.
a, The commercial products Super Glue and an epoxy are shown. b, Curves for soy-mal-tan cured at room temperature for 24 h, 70 °C for 24 h, and 180 °C for 6 h. All substrates here were polished steel.
a, A commercial epoxy shows clean fracture and distinct regions of adhesive versus substrate. b, The soy-mal-tan material shows more complex failure, with stress lines, indicative of ductile behavior. Both substrates were polished steel. The soy-mal-tan adhesive was cured at 180 °C for 6 h.
a, Epoxidized soy oil, malic acid, and tannic acid upon initial mixing at room temperature. b, Soy-mal-tan after 24 h reaction time at 70 °C. Here the adhesive precursor was maintained at 70 °C and viscous, but flowing. c, After the 24 h reaction at 70 °C, cooling to room temperature brought about an increase in viscosity. d, Hardening after a 24 h cure at 180 °C.
a, Initial solution with methyl violet indicator. b, Approximate half-equivalence point reached. c, Equivalence point reached when light green color was present.
a, Infrared spectrum of the final adhesive with all components, epoxidized soy oil, malic acid, and tannic acid. b, Infrared spectrum after a reaction between epoxidized soy oil and malic acid. c, Infrared spectrum of malic acid. Boxes highlight the CO–OH peaks in panels b and c.
Each plot is on the same scale, but offset from each other for comparisons.
a, Resistance of soy-mal-tan to artificial sea water. Bonded pairs of polished aluminum substrates, with 1.2 x 1.2 cm overlap area, were cured in air for 24 h at 70 °C or 6 h at 180 °C and then submerged underwater for varied periods of time at room temperature. The x axis is a log plot in minutes, labelled in hours for clarity. b, Resistance of a commercial epoxy to artificial sea water. Bonded pairs of polished aluminum substrates were cured in air according to the manufacturer’s instructions and then submerged underwater for varied periods of time at room temperature. The x axis is a log plot in minutes, labelled in hours for clarity. c, Testing resistance of soy-mal-tan adhesion to boiling water. These substrates were polished aluminum. In the plots error bars are 90% confidence intervals. For panel a the 180 °C data are from n = 5 samples and the 70 °C data are from n = 10 samples. In panel b the 0 and 1 hour time points are from n = 5 samples with n = 10 samples for the 24 and 168 hour time points.
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Westerman, C.R., McGill, B.C. & Wilker, J.J. Sustainably sourced components to generate high-strength adhesives. Nature 621, 306–311 (2023). https://doi.org/10.1038/s41586-023-06335-7
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DOI: https://doi.org/10.1038/s41586-023-06335-7
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