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CU-Boulder PHYS 7450 - Tethered Polymer Chains

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Tethered polymer chains: surface chemistry and their impact on colloidal and surface propertiesIntroductionTethered polymersIntroductionTheoretical modelsPreparation of brushesIn situ polymerisation methodsBrushes from preformed polymersCharacterisation of surfaces with grafted polymersScaling lawsDensity profilesEffect of tethered chains on colloidal interactionsIntroductionTheoretical modelsExperimental resultsInteraction between colloids with tethered chainsBrushes and small bare particlesBrushes and biocolloidsEffects of tethered chains on wettingOutlookReferencesAdvances in Colloid and Interface Science100–102 (2003) 205–2650001-8686/03/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.PII: S0001-8686Ž02.00061-1Tethered polymer chains: surface chemistry andtheir impact on colloidal and surface propertiesE.P.K. Currie , W. Norde *, M.A. Cohen Stuartab,c, bMaterial Science Center, DSM Research, P.O. Box 18, 6160 MD Geleen, The NetherlandsaLaboratory of Physical and Colloid Chemistry, Wageningen University, P.O. Box 8038,b6700 EK Wageningen, The NetherlandsDepartment of Biomedical Engineering, University of Groningen, A. Deusinglaan 1,c9713 AV Groningen, The NetherlandsReceived 2 May 2002; received in revised form 18 July 2002; accepted 20 August 2002AbstractIn this review the grafting of polymer chains to solid supports or interfaces and thesubsequent impact on colloidal properties is examined. We start by examining theoreticalmodels for densely grafted polymers (brushes), experimental techniques for their preparationand the properties of the ensuing structures. Our aim is to present a broad overview of thestate of the art in this field, rather than an in-depth study. In the second section theinteractions of surfaces with tethered polymers with the surrounding environment and theimpact on colloidal properties are considered. Various theoretical models for such interactionsare discussed. We then review the properties of colloids with tethered polymer chains,interactions between planar brushes and nanocolloids, interactions between brushes andbiocolloids and the impact of grafted polymers on wetting properties of surfaces, using theideas presented in the first section. The review closes with an outlook to possible newdirections of research.䊚 2002 Elsevier Science B.V. All rights reserved.Keywords: End-attached polymers; Brush; Surface; Colloid interaction; Biofouling; Wetting; Proteinadsorption*Corresponding author. Tel.: q31-317-483540; fax: q31-317-483777.E-mail address: [email protected] (W. Norde).206 E.P.K. Currie et al. / Advances in Colloid and Interface Science 100 – 102 (2003) 205–265Contents1.Introduction................................................................................................2062. Tethered polymers......................................................................................... 2082.1. Introduction..........................................................................................2082.2. Theoretical models..................................................................................2092.3. Preparation of brushes .............................................................................2172.3.1. In situ polymerisation methods ............................................................ 2172.3.2. Brushes from preformed polymers ........................................................ 2192.4. Characterisation of surfaces with grafted polymers...........................................2232.4.1. Scaling laws ................................................................................... 2242.4.2. Density profiles ...............................................................................2263. Effect of tethered chains on colloidal interactions .................................................. 2283.1. Introduction..........................................................................................2283.2. Theoretical models..................................................................................2293.3. Experimental results................................................................................2353.3.1. Interaction between colloids with tethered chains ...................................... 2353.3.2. Brushes and small bare particles...........................................................2413.3.3. Brushes and biocolloids ..................................................................... 2423.3.4. Effects of tethered chains on wetting .....................................................2534. Outlook .....................................................................................................256Appendices................................................................................................. 258References.................................................................................................. 2611. IntroductionThe DLVO theory for the stability of lyophobic colloidsw1,2xis a milestonealong the road of colloid science, marking the beginning of a systematic andquantitative investigation of the forces between charged particles. Ever since, it hasbeen the framework for a large body of experimental and theoretical research up tothe present day, and when the precise measurement of surface forces becamepossible, both long range electrostatic repulsion and van der Waals attraction werevery directly confirmed. Of course, refinements and amendments, such as ioncorrelationw3xand surface roughnessw4xeffects are continuously finding their wayinto the theory, and experimental work is extending the knowledge on the propertiesof many kinds of interfaces and ions, as well as improving the techniques to measureforces, but the understanding of colloidal stability in terms of electrostatic repulsionand electrodynamic (dispersive) attraction has come a long way.Electrical double layers are not the only method, however, to impart stability tolyophobic colloids against aggregation. The use of polymers for that purpose isolder than colloid science itself. For example, the Egyptians and Chinese knew howto disperse lamp black and other pigment to obtain inkw5x. Michael Faraday, whomay perhaps be considered as the first colloid chemist, used gelatine to prepare andstabilise gold sols. His samples, dating back to approximately 1850 and on displayin the Royal Institute in London, are still stable after some 150 years. In these207E.P.K. Currie et al. / Advances in


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