Rheology Of Supramolecular Polymers-Books Pdf

Rheology of Supramolecular Polymers
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Ph D Thesis, Doctor of Philosophy, Rheology of Supramolecular Polymers. Aamir Shabbir, September 2016, DTU Chemical Engineering. Department of Chemical and Biochemical Engineering. Technical University of Denmark, Danish Polymer Centre. Building 227, 2800 Kongens Lyngby Denmark, Phone 45 45882161. www dpc kt dtu dk, First and foremost I thank God Almighty for giving me the strength and opportunities.
to accomplish this milestone, This thesis presents the results of my Ph D project carried out at the Danish Poly. mer Centre DPC Department of Chemical and Biochemical Engineering Technical. University of Denmark DTU The work was performed during the period from Oct. 2013 to Sept 2016 under the supervision of Professor Ole Hassager and Associate. Professor Anne Ladegaard Skov at DTU Chemical Engineering This Ph D project was. funded under the Marie Curie Initial Training Network SUPOLEN Supramolecular. assembly of polymeric structures a novel route to enhance soft materials properties. in the European Union Seventh Framework Grant Agreement No 607937. I would like to express my greatest gratitude to my supervisor Prof Ole Hassager. under whose supervision i have learned a lot I also thank Prof Ole Hassager for. introducing me to the fracture of polymer melts Likewise for Asst Prof Nicolas J. Alvarez whose guidance has given me strong experimental problem solving skills I. would like to thank Prof Anne L Skov for inspiring discussions I thank Dr Qian. Huang who has always been there to guide me specially when things didn t work out. I also thank Dr Irakli Javakhishvili for useful scientific discussions and collaboration. on one of the project I would also like to thank Kim Chi Szabo for all the technical. support regarding SEC and DSC, Special thanks to Hanne Pohl and Vibeke H Christiansen for providing keen. assistance regarding administrative matters I also thank all colleagues at the Danish. polymer center for being around specially Sara L Wingstrand Ludovica Hengeller. and Dr Martin Van Drongelen Also i would like to thank the workshop crew for. their technical support on the FSR Ivan H Pedersen Lars M ller and specially S ren. V Madsen for their support on all technical aspects. I would like to thank my SUPOLEN colleagues for providing an amazing company. during the three years Some of the collaborations in particular with Dr Hadi. Goldansaz Dr Guilhem P Baeza Srishti Arora and Salvatore Costanzo have been. very fruitful and have given me the opportunity to learn about materials outside the. scope of my PhD I would also like to thank Victor Boudara Jeremy Brassinne and. Jan Hendricks for useful discussions I thank Dr James Wilson and Dr Arnaud Cadix. for the industrial secondment at Solvay Paris which lasted two months. I would also like to thank Prof Ralph H Colby Penn State University Prof. Evelyne Van Ruymbeke UCL Louvain la Neuve Prof Dimitris Vlassopoulos IESL. FORTH Prof Silvina Cerveny MPC San Sebastian Prof S ren Hvilsted DTU Dr. ii Preface, Quan Chen Chinese Academy of Sciences and all the other authors for the pleasant. collaboration of our joint papers, The days would have passed far more slowly without the support of my friends. Finally I thank my parents for their love and support Without their prayers and. wishes I would never have reached this milestone I also thank my two younger. brothers for their love and support, Aamir Shabbir.
Supramolecular polymers are a broad class of materials that include all polymers. capable of associating via secondary interactions These materials represent an. emerging class of systems with superior versatility compared to classical polymers. with applications in food stuff coatings cost efficient processes or biomedical areas. Design and development of supramolecular polymers using ionic hydrogen. bonding or transition metal complexes with tailored properties requires deep un. derstanding of dynamics both in linear and non linear deformations While linear. rheology is important to understand the dynamics under equilibrium conditions. extensional rheology is relevant during the processing or in the usage of polymers. utilizing supramolecular associations for example acrylic based pressure sensitive. adhesives are subjected to extensional deformations during the peeling where strain. hardening is often desirable Such data is also needed to develop sophisticated multi. scale models that can later be used for predicting the flow behavior and molecular. dynamics of supramolecular networks, This thesis focuses on the experimental rheological study of two class of supramolec. ular polymers namely a hydrogen bonding polymers and b ionic bonding poly. mers hereafter termed as ionomers We study linear and non linear rheology for. a model system of entangled pure poly n butyl acrylate PnBA homopolymer and. four poly acrylic acid PnBA PAA copolymers with varying AA side groups syn. thesized via hydrolysis of pure PnBA homopolymer Second we investigate the. linear viscoelastic response of unentangled 2 ureido 4 1H pyrimidones UPy based. supramolecular networks Third we investigate the rheological response of ionomers. synthesized via condenstation of suflonated pthalates with poly tetramethylene gly. col PTMO both in non linear shear and extensional flows Finally we study brittle. fracture of the above ionomers in extensional flow. Dansk Resume, Supramolekyl re materialer er en bred klasse af materialer som inkluderer poly. merer som selvorganiserer via intermolekyl re eller intramolekyl re kr fter Ma. terialerne besidder en r kke egenskaber som g r dem til attraktive alternativer til. klassiske polymerer f eks til emballage til overfladebehandling eller til medicinske. anvendelser, For at designe og udvikle supramolekyl re polymerer med ion bindinger hy. drogenbindinger eller metal komplex bindinger med nskede egenskaber kr ves. en god forsta else for reologien i ba de line re sa vel som ikke line re deformationer. Medens line r reologi er v sentlig for at forsta dynamik t t pa ligev gt er forl n. gelsesreologi typisk mere vigtig i industrielle processer Sa ledes er det vigtigt at forsta. strain hardening af acryl baserede trykf lsomme kl bere og for at kunne udvikle. multi skala modeller og molekyl r dynamik, Denne afhandling omhandler reologi af to klasser af supramolekyl re polymerer. nemlig a hydrogenbindende polymerer og b ion bindende polymerer herefter. kaldet ionomerer Mere specifikt omhandler den et system med k deindviklet. ren poly n butyl acrylate PnBA homopolymer og fire poly acrylic acid PnBA. PAA copolymerer med varierende AA side grupper syntetiserede via hydrolyse. af ren PnBA homopolymer Dern st unders ges line r viskoelasticitet af ikke. k deindviklet 2 ureido 4 1H pyrimidones UPy baseret supramolecular netw rk. For det tredje unders ges rheologien af ionomerer syntetiseret via kondensation af. suflonerede pthalater med poly tetramethylene glycol PTMO ba de i ikke line r. forskydning og forl ngelse Endelig pr senteres resultater for brudmekanik af. udvalgte systemer i forl ngelse, Abstract iii, Dansk Resume v.
Contents vii, 1 Introduction 1, 1 1 Supramolecular polymers 1. 1 2 Supramolecular polymer rheology 2, 1 3 Shear and Extensional Rheology 4. 1 4 DTU Filament Stretch Rheometer and VADER 1000 5. 1 5 Thesis Outline 6, 1 6 Bibliography 8, 2 The Effect of Hydrogen Bonding on Linear and Nonlinear Rheology of. Entangled Polymer Melts 13, 2 1 Introduction 13, 2 2 Experimental Details 15. 2 3 Results 17, 2 4 Discussion 21, 2 5 Conclusions 26.
2 6 Bibliography 27, 3 Linear Viscoelastic and Dielectric Relaxation Response of Unentangled. UPy based Supramolecular Networks 31, 3 1 Introduction 31. 3 2 Experimental Section 33, 3 3 Results 35, 3 4 Discussion 43. 3 5 Conclusions 51, 3 6 Bibliography 52, 4 Non linear Shear and Uniaxial Extensional Rheology of Polyether Ester. Sulfonate Copolymer Ionomer Melts 57, viii Contents.
4 1 Introduction 57, 4 2 Experimental Section 59, 4 3 Results and Discussion 61. 4 4 Conclusions 71, 4 5 Bibliography 72, 5 Brittle fracture in associative polymers the case of ionomer melts 75. 5 1 Introduction 75, 5 2 Materials and Methods 77, 5 3 Results 78. 5 4 Discussion 82, 5 5 Conclusions 88, 5 6 Bibliography 89. 6 Summarizing chapter 93, 6 1 Bibliography 95, A Joint Author Statements 97.
Introduction, 1 1 Supramolecular polymers, Supramolecular polymers are relatively new class of polymers with attractive groups. that offer reversible interactions and thus the possibility of tuning the properties. on will These associative polymers present superior versatility compared to their. covalent polymeric counterparts They include charged polymers ionomers poly. electrolytes metal ligands Rossow and Seiffert 2014 Mugemana et al 2010. Eisenberg and Kim 1998 Zhang et al 2014 Chen et al 2013 and polymers with. hydrogen bonding Lewis et al 2014 Feldman et al 2009 Nair et al 2008 A. very well known naturally occurring supramolecular system is DNA Cooperative. non covalent interactions such as multiple hydrogen bonding and hydrophobic inter. actions give rise to its unique architecture Other example from nature is spider silk. whose remarkable strength arises from presence of micro crystalline domains formed. by secondary interactions and embedded in a flexible matrix Hirschberg 2001. Amongst the man made materials Nylon is a good example in which hydrogen. bonding between the polymer chains gives rise to exceptional material properties. Hydrogen bonding is the most employed non covalent reversible interaction. to create supramolcular poymeric assemblies Nair et al 2008 The dynamics of. hydrogen bonded transient networks can be significantly altered by changing the. exchange rate between two hydrogen bonding motifs via external stimuli such as. temperature At high temperatures molecular chains can release stress at a fast rate. because of decrease of hydrogen bond life time which can lead to low viscosity melts. This remarkable property thus allows easy processing of such materials for various. applications Yan et al 2012 Alternatively at low temperatures the hydrogen bond. life can be significantly larger than the experimental time scales leading to transient. networks Hydrogen bond strength and density of side groups are two important. control variables that can be used to design tailored supramolecular networks Weak. hydrogen bonding motifs including carboxylic acids and amide groups can increase. melt viscosity and introduce hierarchical structures in polymer melts Lewis et al. 2014 For much stronger supramolecular networks multiple hydrogen bonding. arrays can be exploited Bosman et al 2004 Sijbesma et al 1997 One such. famous building block unit is 2 ureido 4 pyrimidones UPy developed by Beijer. et al 1998 which can dimerize strongly in a self complementary array of quadruple. hydrogen bonds Another remarkable property of hydrogen bonding supramolecular. polymers is the ability to self heal upon contact The use of hydrogen bonding has. large potential in coatings pressure sensitive adhesives and as elastomeric materials. 2 1 Introduction, Figure 1 1 a Metal ligand interactions b Ionic bonding interactions c Hydrogen. bonding interactions, Bosman et al 2004 Cordier et al 2008 Creton 2011. Ionomers represent another class of associative polymers where ionic groups. are covalently attached to the polymer backbone The key feature of ionomers is. that a relatively modest concentration of ionic groups attached to a low dielectric. constant polymer can provide significant changes in physical mechanical and dy. namic properties of a polymer Ionomers are nano structured materials similar to. nanocomposites and block polymers Ionomers have applications in polymer blends. film and packaging coatings and adhesives Zhang et al 2014. Supramolecular assemblies utlizing metal ligand coordination are highly direc. tional and of great strength which have been widely used to build stimuli responsive. polymers The tunable coordination binding strength as well as fascinating elec. trochemical magnetic properties and photo physical properties of the metal ions. and ligands would benefit the application of metallo supramolecular polymers in. material science Yan et al 2012, 1 2 Supramolecular polymer rheology. The linear rheology of supramolecular polymers is very rich and offers opportunities. for property manipulation Understanding the rich dynamics of such associative. polymers is thus interesting from both fundamental and applied standpoints The. rheological response of unentangled suprmolecular polymers is well described using. the modified Rouse model called the sticky Rouse model Chen et al 2013 Ac. cording to this theory reversible associations act as a secondary source of friction. 1 2 Supramolecular polymer rheology 3, for the polymer chains thus delaying the terminal relaxation Leibler et al 1991.
The dynamics of entangled supramolecular polymers is even more complex where. both the topological constraints and association dissociation dynamics play a role. Since these two mechanisms are governed by two different microscopic time scales. internal clocks a thermorheologically complex behaviour is expected Shabbir et al. 2015 van Ruymbeke et al 2010 Stadler et al 2009 Phase separation and aggre. Supramolecular polymers are a broad class of materials that include all polymers capable of associating via secondary interactions These materials represent an emerging class of systems with superior versatility compared to classical polymers with applications in food stuff coatings cost ef cient processes or biomedical areas

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