Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Making waves in a photoactive polymer film

Nature volume 546, pages 632–636 (2017)Cite this article

Subjects

Abstract

Oscillating materials1,2,3,4 that adapt their shapes in response to external stimuli are of interest for emerging applications in medicine and robotics. For example, liquid-crystal networks can be programmed to undergo stimulus-induced deformations in various geometries, including in response to light5,6. Azobenzene molecules are often incorporated into liquid-crystal polymer films to make them photoresponsive7,8,9,10,11; however, in most cases only the bending responses of these films have been studied, and relaxation after photo-isomerization is rather slow. Modifying the core or adding substituents to the azobenzene moiety can lead to marked changes in photophysical and photochemical properties12,13,14,15, providing an opportunity to circumvent the use of a complex set-up that involves multiple light sources, lenses or mirrors. Here, by incorporating azobenzene derivatives with fast cis-to-trans thermal relaxation into liquid-crystal networks, we generate photoactive polymer films that exhibit continuous, directional, macroscopic mechanical waves under constant light illumination, with a feedback loop that is driven by self-shadowing. We explain the mechanism of wave generation using a theoretical model and numerical simulations, which show good qualitative agreement with our experiments. We also demonstrate the potential application of our photoactive films in light-driven locomotion and self-cleaning surfaces, and anticipate further applications in fields such as photomechanical energy harvesting and miniaturized transport.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Azo dyes and their cis-to-trans relaxation.
Figure 2: Mechanism of wave propagation and parameters that influence the propagation speed.
Figure 3: Temperature traces recorded by an infrared thermal camera during wave propagation.
Figure 4: Two example applications, demonstrating rejection of contaminants and oscillatory transport of a framed film.

Similar content being viewed by others

References

  1. Tabata, O., Hirasawa, H., Aoki, S., Yoshida, R. & Kokufuta, E. Ciliary motion actuator using self-oscillating gel. Sensor. Actuat. A 95, 234–238 (2002)

    Article  CAS  Google Scholar 

  2. Murase, Y., Maeda, S., Hashimoto, S. & Yoshida, R. Design of a mass transport surface utilizing peristaltic motion of a self-oscillating gel. Langmuir 25, 483–489 (2009)

    Article  CAS  Google Scholar 

  3. Maeda, S., Hara, Y., Yoshida, R. & Hashimoto, S. Peristaltic motion of polymer gels. Angew. Chem. Int. Ed. 47, 6690–6693 (2008)

    Article  CAS  Google Scholar 

  4. Maeda, S., Hara, Y., Sakai, T., Yoshida, R. & Hashimoto, S. Self-walking gel. Adv. Mater. 19, 3480–3484 (2007)

    Article  CAS  Google Scholar 

  5. Martinez, A. & Smalyukh, I. I. Light-driven dynamic Archimedes spirals and periodic oscillatory patterns of topological solitons in anisotropic soft matter. Opt. Express 23, 4591–4604 (2015)

    Article  ADS  CAS  Google Scholar 

  6. White, T. J. et al. A high frequency photodriven polymer oscillator. Soft Matter 4, 1796–1798 (2008)

    Article  ADS  CAS  Google Scholar 

  7. Yu, Y., Nakano, M. & Ikeda, T. Photomechanics: directed bending of a polymer film by light. Nature 425, 145 (2003)

    Article  ADS  CAS  Google Scholar 

  8. van Oosten, C. L., Harris, K. D., Bastiaansen, C. W. M. & Broer, D. J. Glassy photomechanical liquid-crystal network actuators for microscale devices. Eur. Phys. J. E 23, 329–336 (2007)

    Article  CAS  Google Scholar 

  9. Li, M.-H., Keller, P., Li, B., Wang, X. & Brunet, M. Light-driven side-on nematic elastomer actuators. Adv. Mater. 15, 569–572 (2003)

    Article  CAS  Google Scholar 

  10. Iamsaard, S. et al. Conversion of light into macroscopic helical motion. Nat. Chem. 6, 229–235 (2014)

    Article  CAS  Google Scholar 

  11. Yamada, M. et al. Photomobile polymer materials: towards light-driven plastic motors. Angew. Chem. Int. Ed. 47, 4986–4988 (2008)

    Article  CAS  Google Scholar 

  12. Bandara, H. M. D. & Burdette, S. C. Photoisomerization in different classes of azobenzene. Chem. Soc. Rev. 41, 1809–1825 (2012)

    Article  CAS  Google Scholar 

  13. García-Amorós, J. & Velasco, D. Recent advances towards azobenzene-based light-driven real-time information-transmitting materials. Beilstein J. Org. Chem. 8, 1003–1017 (2012)

    Article  Google Scholar 

  14. van Oosten, C. L., Bastiaansen, C. W. M. & Broer, D. J. Printed artificial cilia from liquid-crystal network actuators modularly driven by light. Nat. Mater. 8, 677–682 (2009)

    Article  ADS  CAS  Google Scholar 

  15. Camacho-Lopez, M., Finkelmann, H., Palffy-Muhoray, P. & Shelley, M. Fast liquid-crystal elastomer swims into the dark. Nat. Mater. 3, 307–310 (2004)

    Article  ADS  CAS  Google Scholar 

  16. Brode, W. R., Gould, J. H. & Wyman, G. M. The relation between the absorption spectra and the chemical constitution of dyes. XXV. Phototropism and cis-trans isomerism in aromatic azo compounds. J. Am. Chem. Soc. 74, 4641–4646 (1952)

    Article  CAS  Google Scholar 

  17. Mol, G. N., Harris, K. D., Bastiaansen, C. W. M. & Broer, D. J. Thermo-mechanical responses of liquid-crystal networks with a splayed molecular organization. Adv. Funct. Mater. 15, 1155–1159 (2005)

    Article  CAS  Google Scholar 

  18. Mita, I., Horie, K. & Hirao, K. Photochemistry in polymer solids. 9. Photoisomerization of azobenzene in a polycarbonate film. Macromolecules 22, 558–563 (1989)

    Article  ADS  CAS  Google Scholar 

  19. Poutanen, M., Ikkala, O. & Priimagi, A. Structurally controlled dynamics in azobenzene-based supramolecular self-assemblies in solid state. Macromolecules 49, 4095–4101 (2016)

    Article  ADS  CAS  Google Scholar 

  20. Serra, F. & Terentjev, E. M. Effects of solvent viscosity and polarity on the isomerization of azobenzene. Macromolecules 41, 981–986 (2008)

    Article  ADS  CAS  Google Scholar 

  21. Vapaavuori, J., Laventure, A., Bazuin, C. G., Lebel, O. & Pellerin, C. Submolecular plasticization induced by photons in azobenzene materials. J. Am. Chem. Soc. 137, 13510–13517 (2015)

    Article  CAS  Google Scholar 

  22. Fang, G. J. et al. Athermal photofluidization of glasses. Nat. Commun. 4, 1521 (2013)

    Article  ADS  CAS  Google Scholar 

  23. Sawa, Y. et al. Shape and chirality transitions in off-axis twist nematic elastomer ribbons. Phys. Rev. E 88, 022502 (2013)

    Article  ADS  Google Scholar 

  24. Konya, A., Gimenez-Pinto, V. & Selinger, R. L. B. Modeling defects, shape evolution, and programmed auto-origami in liquid crystal elastomers. Front. Mater. 3, 24 (2016)

    Article  Google Scholar 

  25. de Haan, L. T. et al. Accordion-like actuators of multiple 3D patterned liquid crystal polymer films. Adv. Funct. Mater. 24, 1251–1258 (2014)

    Article  CAS  Google Scholar 

  26. Naidek, K. P. et al. Ruthenium acetate cluster amphiphiles and their Langmuir-Blodgett films for electrochromic switching devices. Eur. J. Inorg. Chem. 2014, 1150–1157 (2014)

    Article  CAS  Google Scholar 

  27. Stumpel, J. E., Liu, D., Broer, D. J. & Schenning, A. P. H. J. Photoswitchable hydrogel surface topographies by polymerisation-induced diffusion. Chem. Eur. J. 19, 10922–10927 (2013)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported financially by the Netherlands Organization for Scientific Research (NWO; TOP PUNT grant 10018944), the European Research Council (Vibrate ERC, grant 669991), and US National Science Foundation grants DMR 1409658 and CMMI 1436565. A.H.G. acknowledges funding from the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme FP7-2013, grant number 607602. Computing resources provided by the Ohio Supercomputer Center (M.V., A.K., R.L.B.S.) R.L.B.S. acknowledges F. Nazarov for discussions and B. L. Mbanga for his role in developing the Finite Element Method algorithm. The work of D.J.M. forms part of the research programme of the Dutch Polymer Institute (DPI), project 776n.

Author information

Authors and Affiliations

  1. Department of Chemical Engineering and Chemistry, Laboratory for Functional Organic Materials and Devices (SFD), Eindhoven University of Technology, Eindhoven, The Netherlands

    Anne Helene Gelebart, Dirk Jan Mulder & Dirk J. Broer

  2. Institute for Complex Molecular Systems (ICMS), Eindhoven University of Technology, Eindhoven, The Netherlands

    Anne Helene Gelebart, Ghislaine Vantomme, E. W. Meijer & Dirk J. Broer

  3. Chemical Physics Interdisciplinary Program, Liquid Crystal Institute, Kent State University, Kent, Ohio, USA

    Michael Varga, Andrew Konya & Robin L. B. Selinger

Authors
  1. Anne Helene Gelebart
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dirk Jan Mulder
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Michael Varga
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Andrew Konya
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ghislaine Vantomme
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. E. W. Meijer
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Robin L. B. Selinger
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Dirk J. Broer
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

A.H.G. and D.J.M. designed the experiments. A.H.G. studied the macroscopic deformations and analysed the results. D.J.M. synthesized I. G.V. synthesized II. M.V. and A.K. developed the theoretical model. D.J.B. supervised the overall research. E.W.M. participated in the interpretation of the results. R.L.B.S. supervised the theoretical modelling. All authors contributed to the writing of the manuscript.

Corresponding authors

Correspondence to Robin L. B. Selinger or Dirk J. Broer.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

Reviewer Information Nature thanks T. Ikeda, R. Verduzco and Y. Yu for their contribution to the peer review of this work.

Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data figures and tables

Extended Data Figure 1 Synthetic routes for constituent compounds.

Components of the LCN films include AzoPy, I and II.

Extended Data Figure 2 Thermal characterization of the mixtures used in the study.

a, Differential scanning calorimetry scans (second runs, exotherm downwards) showing the phase behaviour of all mixtures investigated. The nematic-to-isotropic transition occurs at 90 °C. b, Differential scanning calorimetry scan of a polymerized sample showing the change in specific heat at the glass transition temperature (Tg). The table summarizes the Tg data of the various polymerized compositions. c, Normalized absorption spectra of the various mixtures investigated.

Extended Data Figure 3 Relaxation kinetics of the azo-derivatives embedded in the LCN.

a–d, Thermal relaxation from the photostationary cis state to the trans state of A6MA (a), I (b), II (c) and DR1A (d) at various temperatures. Here and .

Extended Data Figure 4 Pictures taken at different angles showing the curvatures that were created, inducing the self-shadowing effect.

Scale bar, 5 mm. At 90°, the bump is formed (indicated by the arrow), but because no shadow is created the wave cannot propagate and the film remains in that position.

Extended Data Figure 5 Temperature measured at the front of the wave.

a, Influence of the intensity on the temperature increase at the front of the wave. The red shaded region is a guide to help to visualize the glass transition region. b, Measured temperature for the uniaxially oriented sample. Despite the rubbery character of the films, no motion was observed.

Extended Data Figure 6 Temperature measurements during wave propagation.

a, c, Thermal pictures of the wave taken at different times t. b, Temperature profile over the length of the film (along the black line in a) for the homeotropic-up sample during wave propagation at t = 0 s (black line), t = 0.67 s (dark grey line) and t = 1.40 s (light grey line). d, Temperature profiles over the length of the film (along the black line in c) for the planar-up sample at t = 0 s (black line), t = 0.11 s (dark grey line) and t = 0.22 s (light grey line).

Extended Data Figure 7 1H NMR spectra of the constituent compounds.

a, 1H NMR of the compound AzoPy, which was used to form compound I. b, 1H NMR of compound II.

Extended Data Figure 8 Transmission spectra of the LCN films.

Transmissions (T, expressed as percentages) for compound I (green), compound II (black), A6MA (red), AzoPy (pink) and DR1A (blue) are shown. Thickness, 20 μm. The films containing A6MA, compound I and AzoPy are actuated with 405-nm light. At this wavelength, the transmissions are 6.3%, 4.1% and 8.9%, respectively. The samples containing DR1A and compound II are illuminated with 455-nm light. At this wavelength, the initial transmissions are 26% and 13%, respectively.

Extended Data Table 1 Chemical compositions of the mixtures
Full size table

Supplementary information

Reference experiments

Comparison between a splay aligned sample (left) and two uniaxially aligned samples (planar and homeotropic). Videos are played in real time. (MOV 9844 kb)

Type of deformation obtained when the LCN films is exposed to UV light without any constraint (worm like displacement) and when one constraint point is used (oscillation and tube).

Type of deformation obtained when the LCN films is exposed to UV light without any constraint (worm like displacement) and when one constraint point is used (oscillation and tube). Videos are played in real time. (MOV 18846 kb)

Reference experiments

Comparison between the different molecules investigated. Videos are played in real time. (MOV 14673 kb)

Wave-like propagation with the planar side placed upwards

The incident light comes from the left and the wave propagates toward the opposite direction. Model and experiment are placed side to side to show good agreement. In the second part of the video the thermal effects are shown. Videos are played in real time. (MOV 23391 kb)

Wave like propagation with the homeotropic side placed upwards

The incident light comes from the left and the wave propagates toward the light. Model and experiment are placed side to side to show good agreement. In the second part of the video the thermal effects are shown. Videos are played in real time. (MOV 25149 kb)

Examples of use for the wave propagation

The first part of the video shows that the LCN film carry uphill object much heavier and much bigger than its own dimension. The second part of the video shows the use of the wave for self-cleaning surfaces with the ejection of sand placed at the surface. Videos are played in real time. (MOV 20362 kb)

Light fuelled vehicle. Planar side up

The light comes from the left side and the polymeric film is constrained in a non-responsive frame. Videos are played in real time. (MOV 10702 kb)

Light fuelled vehicle, homeotropic side up

The light comes from the left side and the polymeric film is constrained in a non-responsive frame. Videos are played in real time. (MOV 27077 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gelebart, A., Jan Mulder, D., Varga, M. et al. Making waves in a photoactive polymer film. Nature 546, 632–636 (2017). https://doi.org/10.1038/nature22987

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature22987

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing