The development and study of new smart materials is an emergent research area with high potential applications. In this study, we have fabricated poly(ethyleneimine)/poly(acrylic acid) multilayer films on glass substrates by automated spray-layer-by-layer (spray-LbL) technique. By analyzing the changes in thickness, roughness and elasticity, with fine-tuning of the operational parameters of the spray-LbL system, evident trends of its effect on the multilayer construction were observed. In the case of its mechanical properties, the stability of Young’s modulus (up to 8.25 GPa) from film thickness at this scale was detected, making it variable for other factors such as pH and molecular weight. This work also identified the healability phenomenon that is present in the exponentially grown PEI/PAA samples, based on the reduction in viscosity of the polymer complexes and the interdiffusion of polyelectrolytes at the damaged zones in the presence of water. These properties allow for the assembly of a highly electrically conductive multilayered film by dispersion of a top layer of silver nanowires whose sheet resistance is increased around 5% after multiple damaging events. These experimental results provide new data for the evaluation and design of polyelectrolyte multilayers assembled with a spin-assisted automated spray deposition system to serve as substrates for mechanoelectrical devices which can benefit from its self-healing and modulated mechanical capabilities.
This is a preview of subscription content, log in to check access.
Buy single article
Instant unlimited access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Hara, M, Polyelectrolytes: Science and Technology. Marcel Dekker, New York (1992)
Fang, M, Kaschak, DM, Sutorik, AC, Mallouk, TE, “A ‘Mix and Match’ Ionic-covalent Strategy for Self-Assembly of Inorganic Multilayer Films.” J. Am. Chem. Soc., 119 (50) 12184–12191 (1997)
Huang, X, Bolen, MJ, Zacharia, NS, “Omniphobic Slippery Coatings Based on Lubricant-Infused Porous Polyelectrolyte Multilayers.” ACS Macro Lett., 2 826–829 (2013)
Wang, L, Wang, X, Xu, M, Chen, D, Sun, J, “Layer-by-Layer Assembled Microgel Films with High Loading Capacity: Reversible Loading and Release of Dyes and Nanoparticles.” Langmuir, 24 (5) 1902–1909 (2008)
Decher, G, “Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites.” Science, 277 (5330) 1232–1237 (1997)
Bertrand, P, Jonas, A, Laschewsky, A, Legras, R, “Ultrathin Polymer Coatings by Complexation of Polyelectrolytes at Interfaces: Suitable Materials, Structure and Properties.” Macromol. Rapid Comm., 21 (7) 319–348 (2000)
Cho, J, Hong, J, Char, K, Caruso, F, “Nanoporous Block Copolymer Micelle/Micelle Multilayer Films with Dual Optical Properties.” J. Am. Chem. Soc., 128 (30) 9935–9942 (2006)
Wang, Y, Joshi, PP, Hobbs, KL, Johnson, MB, Schmidtke, DW, “Nanostructured Biosensors Built by Layer-by-Layer Electrostatic Assembly of Enzyme-Coated Single-Walled Carbon Nanotubes and Redox Polymers.” Langmuir, 22 (23) 9776–9783 (2006)
Kang, EH, Jin, P, Yang, Y, Sun, J, Shen, J, “A Facile Room Temperature Layer-by-Layer Deposition Process for the Fabrication of Ultrathin Films with Noncentrosymmetrically Oriented Azobenzene Chromophores.” Chem. Commun., 41 4332–4334 (2006)
Lowman, GM, Tokuhisa, H, Lutkenhaus, JL, Hammond, PT, “Novel Solid-State Polymer Electrolyte Consisting of a Porous Layer-by-Layer Polyelectrolyte Thin Film and Oligoethylene Glycol.” Langmuir, 20 (22) 9791–9795 (2004)
Guldi, DM, Zilbermann, I, Anderson, G, Kotov, NA, Tagmatarchis, N, Prato, M, “Nanosized Inorganic/Organic Composites for Solar Energy Conversion.” J. Mater. Chem., 15 114–118 (2005)
Lynn, DM, “Layers of Opportunity: Nanostructured Polymer Assemblies for the Delivery of Macromolecular Therapeutics.” Soft Matter, 2 269–273 (2006)
Langer, R, “New Methods of Drug Delivery.” Science, 249 (4976) 1527–1533 (1990)
Nakajima, A, Hashimoto, K, Watanabe, T, Takai, K, Yamauchi, G, Fujishima, A, “Transparent Superhydrophobic Thin Films with Self-cleaning Properties.” Langmuir, 16 (17) 7044–7047 (2000)
Spaetha, M, Barthlott, W, “Lotus-Effect: Biomimetic Super-Hydrophobic Surfaces and Their Application.” Adv. Sci. Technol., 60 38–46 (2008)
Koch, K, Bhushan, B, Ensikat, HJ, Barthlott, W, “Self-healing of Voids in the Wax Coating on Plant Surfaces.” Phil. Trans. R. Soc. A, 367 (1894) 1673–1688 (2009)
Li, Y, Chen, S, Wu, M, Sun, J, “Polyelectrolyte Multilayers Impart Healability to Highly Electrically Conductive Films.” Adv. Mater., 24 (33) 4578–4582 (2012)
Hager, MD, Greil, P, Leyens, C, van der Zwaag, S, Schubert, US, “Self-healing Materials.” Adv. Mater., 22 (47) 5424–5430 (2010)
Burattini, S, Greenland, BW, Hayes, W, Mackay, ME, Rowan, SJ, Colquhoun, HM, “A Supramolecular Polymer Based on Tweezer-Type Stacking Interactions: Molecular Design for Healability and Enhanced Toughness.” Chemistry of Materials, 23 (1) 6–8 (2011)
Toohey, KS, Sottos, NR, Lewis, JA, Moore, JS, White, SR, “Self-healing Materials with Microvascular Networks.” Nat Mater, 6 (8) 581–585 (2007)
Shchukin, DG, Mohwald, H, “Self-repairing Coatings Containing Active Nanoreservoirs.” Small, 3 (6) 926–943 (2007)
Shchukin, DG, Zheludkevich, M, Yasakau, K, Lamaka, S, Ferreira, MGS, Mohwald, H, “Layer-by-Layer Assembled Nanocontainers for Self-healing Corrosion Protection.” Adv. Mater., 18 (13) 1672–1678 (2006)
Williams, KA, Boydston, AJ, Bielawski, CW, “Towards Electrically Conductive, Self-healing Materials.” J. R. Soc. Interface, 4 (13) 359–362 (2007)
Caruso, MM, Schelkopf, SR, Jackson, AC, Landry, AM, Braun, PV, Moore, JS, “Microcapsules Containing Suspensions of Carbon Nanotubes.” J. Mater. Chem., 19 6093–6096 (2009)
Huang, X, Bolen, MJ, Zacharia, NS, “Silver Nanoparticle Aided Self-healing of Polyelectrolyte Multilayers.” Phys. Chem. Chem. Phys., 16 10267 (2014)
South, A, Lyon, LA, “Autonomic Self-healing of Hydrogel Thin Films.” Angew. Chem. Int. Ed., 49 (4) 767–771 (2010)
Wang, X, Liu, F, Zheng, X, Sun, J, “Water-Enabled Self-healing of Polyelectrolyte Multilayer Coatings.” Angew. Chem. Int. Ed., 50 (48) 11378–11381 (2011)
Wang, SD, Huang, FH, “Antireflection Coatings Formed from Polyelectrolyte Multilayers on PMMA Substrate.” Surface Engineering, 27 (4) 279–285 (2011)
Schlenof, JB, Dubas, ST, Farhat, T, “Sprayed Polyelectrolyte Multilayers.” Langmuir, 16 (26) 9968–9969 (2000)
Krogman, KC, Lyon, KF, Hammond, PT, “Metal Ion Reactive Thin Films Using Spray Electrostatic LBL Assembly.” J. Phys. Chem. B, 112 (46) 14453–14460 (2008)
Elosua, C, Lopez-Torres, D, Hernaez, M, Matias, IR, Arregui, FJ, “Comparative Study of Layer-by-Layer Deposition Techniques for Poly(Sodium Phosphate) and Poly(Allylamine Hydrochloride).” Nanoscale Res Lett, 8 539 (2013)
Lefort, M, Jierry, L, Boulmedais, F, Benmlih, K, Lavalle, P, Senger, B, Voegel, JC, Hemmerlé, J, Ponche, A, Schaaf, P, “Nanosized Films Based on Multicharged Small Molecules and Oppositely Charged Polyelectrolytes Obtained by Simultaneous Spray Coating of Interacting Species.” Langmuir, 29 (47) 14536–14544 (2013)
Bruening, M, Dotzauer, D, “Polymer Films: Just Spray It.” Nat Mater, 8 (6) 449–450 (2009)
Ven, TGMVD, “Kinetic Aspects of Polymer and Polyelectrolyte Adsorption on Surfaces.” Adv. Colloid Interface Sci., 48 121–140 (1994)
Krogman, KC, Zacharia, NS, Schroeder, S, Hammond, PT, “Automated Process for Improved Uniformity and Versatility of Layer by-Layer Deposition.” Langmuir, 23 3137–3141 (2007)
Abramoff, MD, Magalhaes, PJ, Ram, SJ, “Image Processing with ImageJ.” Biophotonics International, 11 (7) 36–42 (2004)
Lienkamp, K, Kins, CF, Alfred, SF, Madkour, AE, Tew, GN, “Water-Soluble Polymers From Acid-Functionalized Norbornenes.” J. Polym. Sci. A Polym. Chem., 47 1266–1273 (2009)
Ikonen, M, Murtomaki, L, Kontturi, K, “Controlled Complexation of Plasmid DNA with Cationic Polymers: Effect of Surfactant on the Complexation and Stability of the Complexes.” Colloids Surf., B, 66 77–83 (2008)
Izquierdo, A, Ono, SS, Voegel, JC, Schaaf, P, Decher, G, “Dipping Versus Spraying: Exploring the Deposition Conditions for Speeding up Layer-by-Layer Assembly.” Langmuir, 21 (16) 7558–7567 (2005)
Liu, CH, Yu, X, “Silver Nanowire-Based Transparent, Flexible, and Conductive Thin Film.” Nanoscale Res. Lett., 6 75 (2011)
De, S, Higgins, TM, Lyons, PE, Doherty, EM, Nirmalraj, PM, Blau, WJ, Boland, JJ, Coleman, JN, “Silver Nanowire Networks as Flexible, Transparent, Conducting Films: Extremely High DC to Optical Conductivity Ratios.” ACS Nano, 3 (7) 1767–1774 (2009)
The project described was supported by CAT-120 Research Program by Tecnologico de Monterrey, CONACYT-Mexico Award Number (168813) and PAICYT-UANL 2015 Grant Number (IT 489-15).
Funding was provided by Consejo Nacional de Ciencia y Tecnología (Grant No. 169319).
About this article
Cite this article
Ortega, E., Zavala, G., Gracia-Pinilla, M.A. et al. Spray-assisted layer-by-layer assembly of decorated PEI/PAA films: morphological, growth and mechanical behavior. J Coat Technol Res 14, 927–935 (2017) doi:10.1007/s11998-016-9896-z
- Layer-by-layer assembly