Regular Article Surface initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA-ATRP) of 4-vinylpyridine on poly(ethylene terephthalate) Mohamad Maaz a,b , Tamara Elzein a,⇑ , Alice Bejjani a , Nadine Barroca-Aubry b , Bénédicte Lepoittevin b , Diana Dragoe b , Sandra Mazerat b , Bilal Nsouli a , Philippe Roger b,⇑ a Lebanese Atomic Energy Commission, National Council for Scientific Research, CNRS-L, Beirut, Lebanon b Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), UMR 8182, Univ Paris Sud, Université Paris Saclay, 91405, Orsay, France graphical abstract article info Article history: Received 13 February 2017 Revised 30 March 2017 Accepted 31 March 2017 Available online 2 April 2017 Keywords: Poly(ethylene terephthalate) PET Surface-initiated supplemental activator and reducing agent atom transfer radical polymerization SARA ATRP 4-Vinylpyridine 4VP XPS ToF-SIMS abstract Poly(ethylene terephthalate) (PET) substrates were modified by means of surface-initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA-ATRP) of 4-vinylpyridine (4VP). Substrates were pretreated in order to graft chloromethylbenzene (CMB) units capable of initiating the radical polymerization reaction of 4VP units. Surface characterization techniques, including Water Contact Angle (WCA), Attenuated Total Reflection (ATR), X-ray photoelectron spectroscopy (XPS), Atomic Force Microscopy (AFM) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) showed a successful grafting of a stable, smooth and homogenous layer of p4VP. This process offers the advantages of a rapid, simplified and low cost strategy to chemically modify polymer substrates with covalently bonded layer of the pH responsive p4VP for different applications. Moreover, by using TOF- SIMS profiling, we were able to track a density gradient along the z-axis generated by the interpenetrat- ing phases of the different layers of the final modified surface. Fact that we correlated to the various posi- tions of initiation sites within the polyethylenimine (PEI) used for PET aminolysis prior to CMB grafting. Our strategy will be used in future work to graft other polymers for different applications where indus- trial scale viable options are needed. Ó 2017 Elsevier Inc. All rights reserved. http://dx.doi.org/10.1016/j.jcis.2017.03.115 0021-9797/Ó 2017 Elsevier Inc. All rights reserved. ⇑ Corresponding authors. E-mail addresses: tamara.elzein@cnrs.edu.lb (T. Elzein), philippe.roger@u-psud.fr (P. Roger). Journal of Colloid and Interface Science 500 (2017) 69–78 Contents lists available at ScienceDirect Journal of Colloid and Interface Science journal homepage: www.elsevier.com/locate/jcis