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1

Schlindwein, Walkiria Santos. "Conducting polymers and polymer electrolytes." Thesis, University of Leicester, 1990. http://hdl.handle.net/2381/33889.

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Polymers are mostly used as insulator materials. Since the late sixties, two new classes of polymeric materials possessing either ionic or electronic conductivities have been extensively studied. The work carried out in this thesis concerns of the study of polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with divalent salts (ionic conductors) and polypyrroles (PPy) electrochemically and chemically prepared (electronic conductors). Different techniques were used to study their properties including Differential Scanning Calorimetry (DSC), Variable Temperature Polarising Microscopy (VTPM), Extended X-ray Absorption Fine Structure (EXAFS), a.c. Impedance, Cyclic Voltammetry, and Fourier Transform Infra-Red Spectroscopy (FTIR). Water-cast films of PEOn:ZnX2 (X = C1, Br, I) were prepared at a range of stoichiometries. The effects of either residual presence of water or thermal treatment related to the formation of high melting crystalline materials were investigated. The morphology of the zinc halides films differs from similar films cast from acetonitrile/methanol mixtures. The presence of high melting crystalline material in the water cast samples is influenced mostly by the concentration, type of anion and drying procedure applied to the samples. The high melting crystalline materials in the zinc samples are more affected by the drying regime. In some cases, solvent effects can be removed by using a high temperature (e.g. 180°C) drying regime. The presence of water normally depresses the melting temperature of the crystalline structures. Films of PEOn.:CaBr2 and PEOn:NiBr2 cast from water were also examined. The high melting crystalline materials in the calcium samples are more affected by the presence of water. The nickel samples are highly crystalline and the presence of high melting material does not seem to be influenced by either the presence of solvent or the drying procedure. EXAFS was used as a suitable technique to probe the local structure surrounding the cation. The results of the zinc halide samples gave some indication of the interionic and polymer-cation interactions. It was demonstrated that the halogen provides the most substantial contribution for the total EXAFS spectrum and the oxygen contribution is much less significant, except in the case of PEOn:ZnC12 samples. This could be due to the size of the nearest neighbour atoms and/or to the interaction polymer-cation. The presence of neutral "ion pairing" is suggested for the PEOn:ZnBr2 samples. The EXAFS results for the samples containing NiBr2 indicated a strong interaction between polymer-salt and the local structure was dependent on concentration, unlike the zinc samples. The polymerisation of pyrrole was investigated by using chemical and electrochemical oxidation routes. The structural characterisation of the compounds obtained was limited by their insolubility. The electrochemically prepared samples presented higher conductivity than the ones which were chemically prepared. The EXAFS results at the Fe K-edge of the PPyFeCl4 sample, which was prepared by direct chemical oxidation, suggested that the iron is coordinated to oxygens at a distance 1.97 A, chlorines at 3.08 A and perhaps nitrogens at 3.72 A. The iron local structure of the composite PVA/PPy doped with FeCl3 was different from the PPyFeCl4 sample. The iron in the composite sample was coordinated to oxygens at 1.98 A and chlorines at 2.18 A. Alternatively, the presence of a distorted FeCl4- is considered.
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2

Muangpil, Sairoong. "Functionalised polymers and nanoparticle/polymer blends." Thesis, University of Bristol, 2011. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.654111.

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The incorporation of nanoparticles into polydimethylsiloxane polymers either in the form of physical blending or chemical crosslinking has long been studied as it can improve the properties of composite materials. Interactions between the host polymer and the filler particle, filler concentration and conformation of each component are the key factors that influence these properties. Understanding the effect of these factors is of fundamental importance in all practical applications of composite materials. This thesis describes the study of a range of PDMS composites by using a variety of experimental techniques. The main techniques used were spin-spin (T2) relaxation and diffusion NMR spectroscopy, rheology and small-angle neutron scattering (SANS). The molecular mobility of a series of PDMS melts has been studied for both unentangled and entangled molecular weight regimes separated by the critical entanglement molecular weight (Mc) of the polymer. The experimental results revealed the effect of molecular weight and polydispersity of the polymers on their segmental mobility. The dramatic decrease of chain mobility observed at molecular weight above Mc was attributed to the effect of chain entanglements. The effect of nano-sized trimethylsilylated polysilicate resin (R2) on the chain mobility of PDMS in the form of physically blended was also examined. Two different concentrations (17 and 30 vol%) of R2 were incorporated into a wide range molecular weight of PDMS melts. Below Mc, the R2 particle was found to reinforce the PDMS at all particle loadings, whereas a plasticisation effect was observed for high molecular weight PDMS above Mc. This was attributed to a reduction of the degree of the entanglements when polymer chains adsorbed on particles. Chemically bonded composites of PDMS and polyhedral oligomeric silsesquioxane (POSS) were successfully synthesised via hydrosilylation. The length of the PDMS central block was found to affect both the size and the molecular mobility of the triblock polymers. The weight fraction of POSS and substituted groups on POSS were also seen to affect the molecular mobility. Finally, a series ofrandom crosslink polymer films ofPDMS and phenylsilsesquioxane (TPh) was studied by AFM, TEM, SAXS and SANS techniques to investigate the factors influencing the optical clarity of the samples. The degree of swelling and the segmental mobility of the sample films swollen in good and poor solvents were also studied.
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3

Smartt, William Mark. "Formation of microporous polymer via thermally-induced phase transformations in polymer solutions." Diss., Georgia Institute of Technology, 1991. http://hdl.handle.net/1853/32853.

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4

Chester, Shawn Alexander. "Mechanics of amorphous polymers and polymer gels." Thesis, Massachusetts Institute of Technology, 2011. http://hdl.handle.net/1721.1/68898.

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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2011.
Cataloged from PDF version of thesis.
Includes bibliographical references (p. 345-356).
Many applications of amorphous polymers require a thermo-mechanically coupled large-deformation elasto-viscoplasticity theory which models the strain rate and temperature dependent response of amorphous polymeric materials in a temperature range which spans the glass transition temperature of the material. We have formulated such a theory, and also numerically implemented our theory in a finite element program. The material parameters in the theory have been calibrated for poly(methyl methacrylate), polycarbonate, and Zeonex - a cyclo-olefin polymer. The predictive capabilities of the constitutive theory and its numerical implementation have been validated by comparing the results from a suite of validation experiments against corresponding results from numerical simulations. Amorphous chemically-crosslinked polymers form a relatively new class of thermallyactuated shape-memory polymers. Several biomedical applications for thermally-actuated shape-memory polymers have been proposed/demonstrated in the recent literature. However, actual use of such polymers and devices made from these materials is still quite limited. For the variety of proposed applications to be realized with some confidence in their performance, it is important to develop a constitutive theory for the thermo-mechanical response of these materials and a numerical simulation-based design capability which, when supported with experimental data, will allow for the prediction of the response of devices made from these materials under service conditions. We have developed such a theory and a numerical simulation capability, and demonstrated its utility for modeling the thermo-mechanical response of the shape-memory polymer tBA-PEGDMA. An elastomeric gel is a cross-linked polymer network swollen with a solvent, and certain thermally-responsive gels can undergo large reversible volume changes as they are cycled about a critical temperature. We have developed a thermodynamically-consistent continuum-level theory to describe the coupled mechanical-deformation, fluid permeation, and heat transfer of such gels. We have numerically implemented our theory in a finite element program by writing thermo-chemo-mechanically coupled elements. We show that our theory is capable of simulating swelling, squeezing of fluid by applied mechanical forces, and thermally-responsive swelling/de-swelling of such materials.
by Shawn Alexander Chester.
Ph.D.
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5

Mohagheghian, Iman. "Impact response of polymers and polymer nanocomposites." Thesis, University of Cambridge, 2014. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.648854.

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6

Sun, Shuangyi. "Alkoxyphenacyl Polymers: A Novel Photodegradable Polymer Platform." University of Akron / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1424234383.

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7

Cooke, Richard Hunter III. "THE ENHANCEMENT OF PEROXIDE-CURED FLUOROELASTOMER RUBBER TO METAL BONDING." Wright State University / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=wright1377022145.

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8

Michaille, Sylvie. "Photolyse et photo-oxydation des polyesters insatures a l'etat solide." Clermont-Ferrand 2, 1987. http://www.theses.fr/1987CLF2D013.

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L'evolution photolytique et photo-oxydative des polyesters insatures, reticules ou non, exposes a une lumiere polychromatique de longueurs d'onde superieures a 300 nm, a ete etudiee par spectrophotometries ir, irtf, uv-visible. L'influence de chaque parametre d'elaboration a pu etre determinee: nature et concentration des diacides, nature des glycols, nature et concentration des agents reticulants, mode de reticulation. Les mecanismes mettent en jeu l'excitation primaire des groupes fumarates-maleates ou des groupes phtalates, et des reactions radicalaires rendent compte de l'apparition de produits hydroxyles et carbonyles. La photo-isomerisation fumaratemaleate a ete mise en evidence. Par des etudes paralleles de la photochimie du polystyrene et du polybutylene terephtalate a grande longueur d'onde, les differentes origines du photojaunissement ont ete precisees. Le photojaunissement des polyesters insatures depend a la fois des oligomeres styreniques et des unites phtalates. Des processus photolytiques doivent etre impliques au niveau des liaisons ester ainsi que des recombinaisons radicalaires. L'effet de la longueur d'onde d'irradiation a ete apprehende. A 365 nm, la conjugaison phtalatestyrene ne peut etre mise en evidence; a 253,7 nm, des reactions de photopassivation ont pu etre observees. De telles conditions d'irradiation ne sont pas representatives du photo-vieillissement des polyesters insatures reticules
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9

Smallfield, J. A. O. "Metal-polymer and polymer-polymer interfaces : application to conjugated polymer electronic devices /." The Ohio State University, 2002. http://rave.ohiolink.edu/etdc/view?acc_num=osu1343235668.

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10

Yang, Lianyun. "Novel Ferroelectric Behavior in Poly(vinylidene fluoride-co-trifluoroethylene)-Based Random Copolymers." Case Western Reserve University School of Graduate Studies / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=case1431686125.

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11

Quarcoo, Naa Larteokor. "Modeling polymer-colloid phase behavior." Access to citation, abstract and download form provided by ProQuest Information and Learning Company; downloadable PDF file, 152 p, 2007. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:1440615.

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12

Gurun, Bilge. "Deformation studies of polymers and polymer/clay nanocomposites." Diss., Georgia Institute of Technology, 2010. http://hdl.handle.net/1853/37118.

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Polymer clay nanocomposites have been a popular area of materials research since they were first introduced in the 1990s. The inclusion of clays into many different host polymers has been shown to improve the properties of matrix polymers in a number of ways including increased mechanical strength, thermal stability and improved barrier properties while keeping the composite light weight and transparent. Although there is a great deal of published work on the preparation and property measurements of polymer clay nanocomposites, there is no model to design a nanocomposite with a given set of properties for a specific end-use. While it is important to know the structure property relationships of materials, the understanding of how nanocomposites reach their final forms and properties is equally important. A thorough understanding of processing effects on the final structure of polymer clay nanocomposites is still missing. With this perspective, this thesis addresses building structure-processing relationships of polymer clay nanocomposites by analyzing multiaxial deformation behavior using in-situ x-ray scattering techniques. This thesis can be divided into two distinct parts. The first part concerns the design of the in-situ multiaxial deformation device (IMDD) used to create the deformation conditions that polymers go through during processing such as blow molding and thermoforming. The device was designed to overcome several concerns with in situ measurement by maintaining constant sample to detector distance, minimizing the material between the incident beam and the detectors, as well as exposing the same point on the sample throughout deformation. A new design to create biaxial deformation, termed in-situ biaxial deformation device (IBDD), is also introduced in this part of the thesis.. In addition, a new heating unit, attached to IBDD, is designed for higher temperature studies, up to 150°C, to imitate industrial processing conditions more closely. The second part of the thesis addresses the effect of strain, strain rate, and temperature as well as the amount of clay on the polymer morphology evolution during multiaxial deformation.. Two different polymer/clay systems were studied: poly(ethylene)/clay and poly(propylene)/clay. It was observed that the morphological evolution of polyethylene and polypropylene is affected by the existence of clay platelets as well as the deformation temperature and the strain rate. Martensitic transformation of orthorhombic polyethylene crystals into monoclinic crystal form was observed under strain but is hindered in the presence of clay nanoplatelets. The morphology evolution of poly(propylene) crystal structure during multiaxial deformation was more subtle where the most stable α-crystalline form went through strain induced melting. This was more noticeable in the nanocomposites with clays up to 5 wt%. It was also noted that the thickness of the interlamellar amorphous region increased with increasing strain at room temperature due to the elongation of the amorphous chains. The increase in the amorphous layer thickness is slightly higher for the poly(ethylene)/clay nanocomposites compared to neat poly(ethylene) while the increase in the lamellar long spacing is slightly higher for the neat poly(propylene) compared to poly(propylene)/clay nanocomposites. The rate of change in the characteristic repeat distance in both poly(ethylene) and poly(propylene) systems is higher at faster strain rates, at room temperature, where it remained constant during higher temperature deformations. Time dependent recovery after deformation studies have shown that poly(ethylene)/clay system reverts back to its initial configuration. The recovery in the amorphous chains was however observed to take longer in the clay added poly(ethylene)s. Crystalline relaxation was observed to happen almost instantly in the poly(ethylene)/clay system. On the other hand, amorphous chains in the poly(propylene)/clay system did not revert back to the initial configuration in the period of time that the recovery observations were performed while the crystalline configuration recovered back almost fully in the given time.
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13

Xie, Yixuan. "Synthesis And Characterization of Mannose-grafted Peptide-Like Polyesters." University of Akron / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1460383230.

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14

Chirowodza, Helen. "Polymer-clay nanocomposites prepared by RAFT-supported grafting." Thesis, Stellenbosch : Stellenbosch University, 2012. http://hdl.handle.net/10019.1/71914.

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Thesis (PhD)--Stellenbosch University, 2012.
ENGLISH ABSTRACT: In materials chemistry, surface-initiated reversible deactivation radical polymerisation (SI-RDRP) has emerged as one of the most versatile routes to synthesising inorganic/organic hybrid materials consisting of well-defined polymers. The resultant materials often exhibit a remarkable improvement in bulk material properties even after the addition of very small amounts of inorganic modifiers like clay. A novel cationic reversible addition–fragmentation chain transfer (RAFT) agent with the dual purpose of modifying the surface of Laponite clay and controlling the polymerisation of monomer therefrom, was designed and synthesised. Its efficiency to control the polymerisation of styrene was evaluated and confirmed through investigating the molar mass evolution and chain-end functionality. The surface of Laponite clay was modified with the cationic chain transfer agent (CTA) via ion exchange and polymerisation performed in the presence of a free non-functionalised CTA. The addition of the non-functionalised CTA gave an evenly distributed CTA concentration and allowed the simultaneous growth of surface-attached and free polystyrene (PS). Further analysis of the free and grafted PS using analytical techniques developed and published during the course of this study, indicated that the free and grafted PS chains were undergoing different polymerisation mechanisms. For the second monomer system investigated n-butyl acrylate, it was apparent that the molar mass targeted and the monomer conversions attained had a significant influence on the simultaneous growth of the free and grafted polymer chains. Additional analysis of the grafted polymer chains indicated that secondary reactions dominated in the polymerisation of the surface-attached polymer chains. A new approach to separating the inorganic/organic hybrid materials into their various components using asymmetrical flow field-flow fractionation (AF4) was described. The results obtained not only gave an indication of the success of the in situ polymerisation reaction, but also provided information on the morphology of the material. Thermogravimetric analysis (TGA) was carried out on the polymer-clay nanocomposite samples. The results showed that by adding as little as 3 wt-% of clay to the polymer matrix, there was a remarkable improvement in the thermal stability.
AFRIKAANSE OPSOMMING: Oppervlakgeïnisieerde omkeerbare deaktiveringsradikaalpolimerisasie (SI-RDRP) is een van die veelsydigste roetes om anorganiese/organiese hibriedmateriale (wat bestaan uit goed-gedefinieerde polimere) te sintetiseer. Die produk toon dikwels ʼn merkwaardige verbetering in die makroskopiese eienskappe – selfs na die toevoeging van klein hoeveelhede anorganiese modifiseerders soos klei. ʼn Nuwe kationiese omkeerbare addisie-fragmentasie kettingoordrag (RAFT) middel met die tweeledige doel om die modifisering van die oppervlak van Laponite klei en die beheer van die polimerisasie van die monomeer daarvan, is ontwerp en gesintetiseer. Die klei se doeltreffendheid om die polimerisasie van stireen te beheer is geëvalueer en bevestig deur die molêre massa en die funksionele groepe aan die einde van die ketting te ondersoek. Die oppervlak van Laponite klei is gemodifiseer met die kationiese kettingoordragmiddel (CTA) deur middel van ioonuitruiling en polimerisasie wat uitgevoer word in die teenwoordigheid van ʼn vrye nie-gefunksionaliseerde CTA. Die toevoeging van die nie-gefunksionaliseerde CTA het ʼn eweredig-verspreide konsentrasie CTA teweeggebring en die gelyktydige groei van oppervlak-gebonde en vry polistireen (PS) toegelaat. Verdere ontleding van die vrye- en geënte PS met behulp van analitiese tegnieke wat ontwikkel en gepubliseer is gedurende die verloop van hierdie studie, het aangedui dat die vry- en geënte PS-kettings verskillende polimerisasiemeganismes ondergaan. n-Butielakrilaat is in die tweede monomeer-stelsel ondersoek en dit was duidelik dat die molêre massa wat geteiken is en die geënte polimeerkettings. ʼn Nuwe benadering tot die skeiding van die anorganiese/organiese hibriedmateriale in hulle onderskeie komponente met behulp van asimmetriese vloeiveld-vloei fraksionering (AF4) is beskryf. Die resultate wat verkry is, het nie net 'n aanduiding gegee van die sukses van die in-situ polimerisasiereaksie nie, maar het ook inligting verskaf oor die morfologie van die materiaal. Termogravimetriese analise (TGA) is uitgevoer op die polimeer-klei nanosaamgestelde monsters. Die resultate het getoon dat daar 'n merkwaardige verbetering in die termiese stabiliteit was na die toevoeging van so min as 3 wt% klei by die polimeermatriks.
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15

Markotsis, Martin G. School of Chemical Engineering &amp Industrial Chemistry UNSW. "Morphological studies of sbs based interpenetrating polymer networks." Awarded by:University of New South Wales. School of Chemical Engineering and Industrial Chemistry, 2005. http://handle.unsw.edu.au/1959.4/32833.

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Interpenetrating polymer networks (IPNs) of polystyrene-polybutadiene-polystyrene (SBS) block copolymers and polystyrene (PS) were prepared using sequential network formation with the polybutadiene (PB) of the SBS crosslinked thermally and the styrene network formed thermally or by ??-radiation. The use of ??-radiation to cure the added PS network at room temperature successfully avoided thermal degradation of the butadiene segments within the SBS which had been observed in earlier studies. Both linear SBS and radial SB4 IPNs were studied to compare the influence of linear or branched block copolymers on the IPN morphology. The molecular morphology was examined using a suite of techniques including thermal analysis (DSC and DMA), transmission electron microscopy (TEM), atomic force microscopy (AFM) and smallangle X-ray and neutron scattering (SAXS and SANS). The primary SBS/SB4 network morphology was found to dominate the IPN morphology with the secondary styrene network limited to selectively swelling the PS domains. The linear SBS IPNs displayed a more ordered morphology than the radial SB4 IPNs, and this morphology was investigated in pseudo three-dimensions by sectioning samples in two perpendicular directions. The morphology was found to be consistent with thermally formed systems prepared in previous studies, and contained styrenic domains of 20-50 nm within a continuous butadiene matrix. The weight of evidence suggested that the lamella structure dominated the linear SBS IPNs and a cylindrical structure for the radial SB4 IPNs. Maximum values of tensile strength and elongation at break (20 MPa and 140% respectively) were observed in samples with a styrene cure ??-radiation dose of 200 kGy. The SANS analysis of these polymer systems was expanded to investigate the thermal formation of the added PS network in real time. Time-resolved SANS allowed the development of nanostructures in the bulk samples to be measured, and compared to previous time-independent TEM studies on thin sections. The formation of the styrene network was most noticeably observed in a linear SBS IPN system, in which an increase in long-range order was observed and attributed to movement of styrene monomer into the styrenic domains and sharpening of the phase boundaries between the PS and the PB regions.
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16

Vaughan, Asa Dee Byrne Mark E. "Reaction analysis of templated polymer systems." Auburn, Ala., 2008. http://hdl.handle.net/10415/1538.

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17

Dean, Katherine (Katherine Maree) 1974. "Epoxy-dimethacrylate interpenetrating polymer networks." Monash University, School of Physics and Materials Engineering, 2002. http://arrow.monash.edu.au/hdl/1959.1/7791.

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18

Dean, Katherine(Katherine Maree) 1974. "Epoxy-dimethacrylate interpenetrating polymer networks." Monash University, School of Physics and Materials Engineering, 2002. http://arrow.monash.edu.au/hdl/1959.1/8231.

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19

Coutterez, Claire. "Synthèse, caractérisation et étude des propriétés d'oligomères et polymères hétéroarylène vinylènes." Grenoble INPG, 1998. http://www.theses.fr/1998INPG0163.

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Le travail de cette these a concerne la synthese, la caracterisation et l'etude de proprietes d'usage de structures oligomeres et polymeres conjuguees. L'originalite de ces travaux reside d'une part dans l'utilisation d'heterocycles furaniques et thiopheniques comme elements constitutifs des chaines et d'autre part, dans le fait que de nombreux composes oligomeres ont ete cibles, isoles et caracterises. Les possibilites d'application de ces materiaux dans les domaines touchant a l'electronique (conducteurs ou semi-conducteurs), a l'optique (cristaux liquides) et a la luminescence photo- et electroinduite, ont ete ensuite explorees. Ces recherches se divisent en cinq themes : (i) etude des reactions de polycondensation en milieu basique du 5-methyl furfural et du 5-2-(5-methyl furyl vinylene)furfural, avec caracterisation precise des oligo(furylene vinylene)s resultants et des polymeres correspondants. Etude des proprietes de conduction electronique apres dopage a l'iode. Etude de la photoluminescence. (ii) synthese et caracterisation d'oligo(heteroarylene vinylene)s furaniques, thiopheniques et mixtes par condensation en milieu basique de monomeres furaniques et/ou thiopheniques. (iii) synthese et caracterisation de bases de schiff ene-heterocycliques/aromatiques mono- et difonctionnelles. Etudes des proprietes thermiques et plus particulierement du comportement mesogene de ces structures. (iv) preparation d'electrolytes polymeres reticules (macrobases de schiff) : formation photochimique du reseau via la presence intrinseque d'unites -2,5-fu-ch = ch-fu-2,5-chromophores. Etude de la conductivite ionique apres dopage avec des sels de lithium. (v) preparation de polyacetylenes monosubstitues par des esters 2-furoiques dans le but d'obtenir des materiaux solubles et possedant, sous forme de membrane des proprietes de permeabilite selective des fluides.
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Faul, C. F. J. (Charles Frederick James). "Directed synthesis of polymer mesostructures." Thesis, Stellenbosch : Stellenbosch University, 2000. http://hdl.handle.net/10019.1/51729.

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Thesis (PhD)--Stellenbosch University, 2000.
ENGLISH ABSTRACT: The objective of this research was to produce discrete, nano-shaped polymeric structures on the same length scale as, or one to one copies of, templates, deformable templates or structure-directing hosts. Polymerisation of hydrophobic organic monomers in high concentration surfactant solutions, leads to the formation of shaped particles (rod-like, plank-like and ribbon-like particles) in the micrometer size range. The origin of these regularly shaped particles was investigated. It is proposed that they were not polymeric in nature, but formed by the crystallisation of the surfactant in the presence of electrolytes and ethanol as solvent. The polymeric particles that were formed were found to be of spherical shape, and no directing of the shape was detected. Mesostructured hosts were then investigated for their possible use as structure-directing agents. A series of polyelectrolyte-surfactant complexes of polydiallylammonium chloride with sodium sulphate surfactants (ranging from C10 to C16) were synthesised and characterised in terms of their thermal, mechanical and structural properties. The complex of polydiallylammonium chloride and sodium dodecyl sulphate was selected as an appropriate self-assembled model system for investigations into the structure-directing properties of these new materials. The polymerisation of hydrophobic organic monomers, such as styrene and the di-functional monomer m-diisopropenylbenzene (m-DIB), within the above mesoscopically structured polyelectrolyte-surfactant complex as host, lead to the formation of unconventionally shaped polymeric particles. The influence of the presence of monomers and guest polymers on the phase morphology of the host was investigated by small angle X-ray analyses (SAXS) and dynamic mechanical analyses (DMA). SAXS analyses showed that these new, stable hosts can hold up to 17 % guest polymer before phase disruption is encountered. These findings were supported by changes in the mechanical properties, as determined by DMA. The transmission electron microscopy (TEM) images of particles obtained after polymerisation showed very clearly that the poly-(m-DIB) did not form a continuous copy of the 3D hexagonal structure of the host, but rather colloidal copies of a part of the host structure that swelled the most. The shapes of the polymer mesostructures were dictated by the morphology of the phase of the structure-directing host, to produce nanosized wires (dimensions 4 by 100 nm), cigar-shaped particles (dimensions 8 by 50 nm) and fibrillar bent shapes (larger than 200 nm), as revealed by TEM. According to literature these are the first shaped, polymer nano-particles produced in a soft, selfassembled, organic templating host.
AFRIKAANSE OPSOMMING: Die doel van hierdie navorsing was om diskrete, nano-gevormde polimeriese partikels van dieselfde lengteskaal as, of direkte een tot een kopië van, 'n templaat, 'n vervormbare of struktuur-rigtende gasheersisteem te produseer. Die polimerisasie van hidrofobiese organiese monomere in seep oplossings van hoë konsentrasie, het gelei tot die produksie van gevormde partikels. Die oorsprong van hierdie partikels is ondersoek. Dit word voorgestel dat die partikels nie polimeries van aard is nie, maar gevorm is deur die kristallisasie van die seep in die teenwoordigheid van elekotroliete en etanol as oplosmiddel. Die polimeriese partikels wat wel geproduseer is, was sferies in vorm, en geen rigtende invloed op die vorm van die partikels is waargeneem nie. Meso-gestruktureerde gasheersisteme is ook ondersoek vir moontlike gebruik as struktuur-rigtende agente. 'n Reeks poliëlektroliet-seep komplekse van polidiallielammoniumchloried en natriumsulfaat sepe (van C10 tot C16) is gesintetiseer en gekarakteriseer in terme van hul termiese, meganiese en strukturele eienskappe. Die kompleks van polidiallielammoniumchloried en natrium dodekielsulfaat is gekies as 'n toepaslike self-organiserende modelsisteem vir die ondersoeke na die struktuur-rigtende eienskappe van hierdie nuwe materiale. Polimerisasie van hidrofobiese organiese monomere, soos byvoorbeeld stireen en die di-funksionele monomeer m-di-isopropenielbenseen (m-DIB), in hierdie mesoskopies-gestruktureerde poliëlektroliet-seep kompleks, het gelei tot die vorming van nie-konvensionele gevormde polimeriese partikels. Die invloed van die teenwoordigheid van monomere en gaspolimere op die fasemorfologie van die gasheersisteem is ondersoek d.m.v. kleinhoek X-straal diffraksie (Eng. SAXS) en dinamiese meganiese analise (DMA). SAXS analises het aangetoon dat hierdie nuwe, stabiele gasheersisteem tot 17 % gaspolimeer kan inkorporeer voordat fasevernietiging plaasvind. Hierdie resultate is verder ondersteun deur veranderinge in die meganiese eienskappe soos waargeneem deur DMA. Transmissie elektronmikroskopie (TEM) afbeeldinge van partikels geïsoleer na polimerisasie het baie duidelik gewys dat, in die geval van poli-(m-DIB), die gaspolimeer nie 'n kontinue kopie van die drie dimensionele heksagonale struktuur van die gasheersisteem produseer nie. Daar word eerder 'kolloïdale kopieë' van dele van die gasheersisteem wat die meeste swel gevorm. Die vorms van die polimeer mesostrukture word dus bepaal deur die morfologie van die fase van die struktuur-rigtende gasheer, om nanogrootte draadjies (dimensies 4 x 100 nm), sigaarvormige partikels (8 x 50 nm) en fibrillêre gebuigde vorms (groter as 200 nm) te vorm, soos waargeneem met TEM. Volgens die literatuur is hierdie die eerste geval van gevormde polimeer nanopartikels geproduseer in 'n self-organiserende templaat gasheersisteem.
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21

Houghton, Kim ? "Interdiffusion at polymer-polymer interfaces." Thesis, Durham University, 2005. http://etheses.dur.ac.uk/2869/.

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There is not an extensive understanding of diffusion behaviour between chemically different polymers, especially where polymers are partially compatible. Nuclear reaction analysis has been used to observe the diffusion of molten DPEO into glassy PMMA where both polymers are above their entanglement molecular weight. The observed slowing down of diffusion of DPEO may be due to concentration dependent changes m interaction parameter or blend glass transition temperature, Tg. Small angle neutron scattering was used to find the interaction parameter χ, at the temperatures above the melting temperature (Tm) of DPEO but below the Tg of PMMA. The blend exhibited upper critical solution temperature behaviour, enthalpic interactions were dominant and/was found to be concentration dependent. Elastic recoil detection showed that glassy PMMA was quickly dissolved into molten DPEO and subsequently into the evolving DPEO/PMMA blend. The rate of increase of blend PMMA volume fraction (ψPMMA) decreases with increasing volume fraction. DPEO/PMMA diffusion couples can be described by both Fickean and limited supply case II diffusion. PMMA was substituted with a block copolymer polystyrene-b-poly(methylmethacrylate) (PS-PMMA). Polystyrene is immiscible with DPEO and PMMA, however diffusion behaviour was similar to that of pure PMMA with DPEO. PS-PMMA flux into the growing blend was similar to a higher molecular weight than the PMMA block present. Neutron reflectivity was employed to analyse interfacial concentration profiles with better resolution than is possible with ion beam analysis. For the anneal times utilized the diffusion was limited to movement of only a portion of the polymer chain. Bilayers were fitted by a model which included a growing precursor layer with ΨDΡΕΟ- 0.1 and a developing broadening between this layer and DPEO. The copolymer did not diffuse to a distance greater than the radius of gyration of the polymer components.
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22

Guo, Molin. "PROCESSING-STRUCTURE-PROPERTY RELATIONSHIPS INCO-CONTINUOUS POLYMER BLENDS AND COMPOSITES." Case Western Reserve University School of Graduate Studies / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=case1593786851492932.

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23

Chernykh, Andrey. "Main Chain Type Benzoxazine Polymers for High Performance Applications." Cleveland, Ohio : Case Western Reserve University, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=case1232733414.

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24

Pereira, Marcia Rodrigues. "FTIR-ATR studies on polymer/polymer and polymer/liquid interfaces." Thesis, Durham University, 1994. http://etheses.dur.ac.uk/5551/.

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Fourier Transform Infrared Attenuated Total Reflection Spectroscopy (FTIR-ATR) has been employed to study polymer laminates composed of poly (methylmethacrylate) (PMMA) and poly(vinyl alcohol) (PVOH) using different base layer thicknesses and different angles of incidence on a ZnSe substrate. By varying the "barrier" layer of PMMA it has been confirmed that different effective penetration depths into the PVOH are achieved, in very good agreement with the calculated electric field as a function of distance away from the substrate surface. These results show that the two-layered model system can be successfully employed to provide a semi-quantitative depth profile of the laminate. Following the FTIR-ATR study on polymer/polymer interface we have demonstrated how the evanescent field absorption from a IR beam can also be used to monitor in situ the molecular interaction at polymer/liquid interfaces. The chosen system was a series of sulphonated polyethersulphones (SPES) and water. The v(_s)(SO(_3)) and V(_a)(SO(_3)) vibrational modes were monitored as the degree of hydration was varied. It has been found that the v(_3)(SO(_3)) mode increases with hydration suggesting that, with hydration the sulphonic acid groups of SPES are dissociated into SO(_3) ions. It has been found that changes also occur in the benzene ring vibrational band that are dependent on the degree of hydration. Spectral subtraction has been employed to highlight changes in the V(_a)(SO(_3)) mode which were not readily observed in the raw spectra due to overlapping bands. The particular behaviour of V(OH) vibrational mode of water molecules has also been analysed. The main conclusion in this case was that the average hydrogen bond strength of the sorbed water is considerable lower than that in pure water. This would favour an efficient flux of water through the membrane. A method based on monitoring the time dependent change in the v(OH) mode of water has been developed to calculate the diffusion of water on SPES membranes. After reaching a steady state, the normalised absorbance plot versus time has been used for numerical evaluation. Two models have been developed, one for Fickian diffusion and another for the dual sorption mode. The experimental results show a much better agreement for the second model. The diffusion coefficient values have been calculated for different samples and interesting variations of the diffusion coefficient as a function of sulphonation level, solvent and film thickness have been analysed in detail.
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25

Lin, Jian. "Novel Lithium Salt and Polymer Electrolytes for Polymer Lithium Batteries." Case Western Reserve University School of Graduate Studies / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=case1215572988.

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26

Gao, Yuan. "Characterization of polymers and supramolecular protein-polymer bioconjugates using mass spectrometry." University of Akron / OhioLINK, 2021. http://rave.ohiolink.edu/etdc/view?acc_num=akron1619735971168192.

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27

Zheng, Yexin. "MOLECULAR DYNAMICS SIMULATION STUDY OF NONLINEAR MECHANICAL BEHAVIOR FOR POLYMER GLASSES AND POLYMER RHEOLOGY." University of Akron / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=akron1595776504507743.

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28

Joyce, Steven John. "The topological trapping of cyclic polymers into polymer networks." Thesis, University of York, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.306470.

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29

Jezzard, Peter. "Nuclear magnetic resonance imaging of polymers and polymer-composites." Thesis, University of Cambridge, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.277832.

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30

Sen, Mustafa Yasin. "Green Polymer Chemistry: Functionalization of Polymers Using Enzymatic Catalysis." University of Akron / OhioLINK, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=akron1258422775.

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31

Zhao, Zhichen. "Understanding melt-deformation effect on mechanical behavior of polymer glasses." University of Akron / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=akron1555001830982788.

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32

Wang, Xiaoteng. "NANOIMPRINTING-DIRECTED ASSEMBLY OF POLYMER-GRAFTED NANOPARTICLES IN POLYMER THIN FILMS." University of Akron / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=akron1568723039135387.

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33

Su, Hsin-Wei. "Controlling Polymer Degradability Through Mechanophore Incorporation and Activation." University of Akron / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=akron158685923268314.

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34

Bailly, Nathalie. "N-vinylpyrrolidone-vinyl acetate block copolymers as drug delivery vehicles." Thesis, Stellenbosch : Stellenbosch University, 2012. http://hdl.handle.net/10019.1/20133.

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Thesis (PhD)--Stellenbosch University, 2012.
ENGLISH ABSTRACT: The primary aim of this study was to investigate the feasibility of the amphiphilic block copolymer poly((vinylpyrrolidone)-b-poly(vinyl acetate)) (PVP-b-PVAc) as a vehicle for hydrophobic anti-cancer drugs. PVP-b-PVAc block copolymers of constant hydrophilic PVP block length and varying hydrophobic PVAc block lengths were synthesized via xanthate-mediated controlled radical polymerization (CRP). The methodology consisted of growing the PVAc chain from a xanthate end-functional PVP. In an aqueous environment the amphiphilic block copolymers selfassembled into spherical vesicle-like structures consisting of a hydrophobic PVAc bilayer membrane, a hydrophilic PVP corona and an aqueous core. The self-assembly behaviour and the physicochemical properties of the self-assembled structures were investigated by 1H NMR spectroscopy, fluorescence spectroscopy, transmission electron microscopy (TEM) and dynamic and static light scattering. Drug loading studies were performed using a model hydrophobic drug, clofazimine, and a common anti-cancer drug paclitaxel (PTX) to evaluate the potential of the PVP-b-PVAc block copolymers for drug delivery,. Clofazimine and PTX were physically entrapped into the hydrophobic domain of the self-assembled PVP-b-PVAc block copolymers via the dialysis method. The drug-loaded PVP-b-PVAc block copolymers were characterized regarding particle size, morphology, stability and drug loading capacity in order to assess their feasibility as a drug vehicle. The polymer vesicles had a relatively high drug loading capacity of 20 wt %. The effect of the hydrophobic PVAc block length on the drug loading capacity and encapsulation efficiency were also studied. Drug loading increased with increasing the hydrophobic PVAc block length. The effect of the drug feed ratio of clofazimine and PTX on the drug loading capacity and encapsulation efficiency were also investigated. The optimal formulation for the drug-loaded PVP-b-PVAc was determined and further investigated in vitro. The size stability of the drugloaded PVP-b-PVAc block copolymers was also assessed under physiological conditions (PBS, pH 7.4, 37 °C) and were stable in the absence and presence of serum. PVP-b-PVAc block copolymers were tested in vitro on MDA-MB-231 multi-drug-resistant human breast epithelial cancer cells and normal MCF12A breast epithelial cells to provide evidence of their antitumor efficacy. In vitro cell culture studies revealed that the PVP-b-PVAc drug carrier exhibited no cytotoxicity towards MDA-MB-231 and MCF12A cells, confirming the biocompatibility of the PVP-b-PVAc carrier. In vitro cytotoxicity assays using clofazimine-PVPb- PVAc formulations showed that when MDA-MB-231 cells were exposed to the formulations, an enhanced therapeutic effect was observed compared to the free drug. Cellular internalization of the PVP-b-PVAc drug carrier was demonstrated by fluorescent labeling of the PVP-b-PVAc carrier. Fluorescence microscopy results showed that the carrier was internalized by the MDAMB- 231 cells after 3 hours and localized in the cytoplasm and the perinuclear region. Overall, it was demonstrated that PVP-b-PVAc block copolymers appear to be promising candidates for the delivery of hydrophobic anti-cancer drugs.
AFRIKAANSE OPSOMMING: Die studie is gebaseer op die gebruik van amfifieliese blokkopolimere van poli((Nvinielpirolidoon)- b-poli(vinielasetaat)) (PVP-b-PVAc) as potensiële geneesmiddeldraers. PVP-b-PVAc blokkopolimere van konstante hydrofiliese bloklengte en verskillende hydrofobiese bloklengte is voorberei via die RAFT/MADIX-proses. Blokkopolimere met vinielasetaat is vanaf poli(N-vinielpirolidoon) met ‘n xantaatendfunksie voorberei. In ‘n wateromgewing vorm die PVP-b-PVAc blokkopolimere vesikel strukture met ‘n hydrofobiese membraan en ‘n hydrofiliese mantel. Die fisies-chemiese eienskappe van die PVP-b-PVAc blokkopolimere is gekarakteriseerd met gebruik van KMR spektroskopie, fluoresent spektroskopie, transmissie elektronmikroskopie (TEM) en dinamiese en statiese lig verstrooiing. Die potensiaal van PVP-b-PVAc as ‘n geneesmiddeldraer is ondersoek deur gebruik te maak van die hydrofobiese geneesmiddel, clofazimine, en ‘n anti-kanker geneesmiddel, paclitaxel. Clofazimine en paclitaxel is ge-inkapsuleer in die hydrofobiese gedeelte van die blokkopolimere via die dialise-metode. Clofazimine-PVP-b-PVAc en paclitaxel-PVPb- PVAc blokkopolimere is gekarakteriseerd met betrekking tot die partikel grootte, morfologie, stabiliteit en laai kapasitiet om die PVP-b-PVAc blokkopolimere as geneesmiddeldraers te evalueer. Die PVP-b-PVAc geneesmiddeldraer het ‘n relatiewe hoë laai kapsiteit van 20 gew % aangetoon. Die invloed van die bloklengte op die laai kapasitiet is ook ondersoek en beskryf. ‘n Toename in die laai kapasitiet is gesien met ‘n toename in die hydrofobiese bloklengte. Die invloed van die hoeveelheid geneesmiddel op die laai kapasitiet en die inkapsuleer doeltreffendheid is ook ondersoek. Die optimale formulasie is gevind en verder gebruik vir in vitro studies. Die stabiliteit van die geneesmiddeldraer in fisiologiese omstandighede (pH 7.4, 37 °C) is ook beskryf. Resultate toon aan dat die sisteem stabiel is onder hierdie omstandighede in die afwesigheid en aanwesigheid van serum. In vitro eksperimente is op MCF12A epiteel-borsselle en MDA-MB-231 epiteelborskankerselle getoets om die anti-tumoraktiwiteit te ondersoek. Resultate toon aan dat die PVP-b-PVAc geen sitotoxiese effek op die selle het nie, wat aandui dat die polimere bioverenigbaar is. Verder is dit bewys dat die PVP-b-PVAc geneesmiddel formualsie ’n hoër sitotoxisiteit besit as die vry-geneesmiddel. Fluoresent studies het aangetoon dat die geneesmiddeldraer na 3 uur opgeneen word deur MDA-MB231 selle en gelokaliseerd is in die sitoplasma en in die omgewing van die kern van die selle. In die algemeen is dit aangetoon dat PVP-b-PVAc blokkopolimere potensiële kandidate vir die lewering van hydrofobiese geneesmiddels is.
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35

Qu, Haoran. "SOLUTION SELF-ASSEMBLY OF HEXAETHYLENE GLYCOL-FUNCTIONALIZED POLYHEDRAL OLIGOMERIC SILSESQUIOXANE (GPOSS) TETHERED WITH POLYSTYRENE CHAIN." University of Akron / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=akron1486638275556455.

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36

Zartman, Gregory D. "The Effects of Melt Stretching on the Mechanical Behavior of Polymer Glasses." University of Akron / OhioLINK, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=akron1342409357.

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37

Li, Mingxuan. "Self-Assemble of Novel Discotic Nano-Molecules Based on Polyhedraloligomericsilsesquioxanes." University of Akron / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=akron1399242960.

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38

Wang, Yi. "The Synthesis and Characterization of Amphiphilic Poly(Ethylene Oxide)-Block-Poly(Octadecyl Acrylate) Block Copolymers." University of Akron / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=akron1399491109.

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39

Zhu, Sunsheng. "Novel Approach to Polyhedral Oligmeric Silsesquioxane-Based Giant Surfactants Basd on Thiol-Michael Addition "Click" Reaction." University of Akron / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=akron1399555570.

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40

Chu, Yang. "Enhancement of Photocatalytic Activity by Site Poisoning Platinum Doped Titanium Dioxide." University of Akron / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=akron1417454495.

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41

Chen, Junyi. "Oligo(ß-Alanine)-Grafted Butyl Rubber (IIR) with Mixed O(ligo(ß-Alanine) Lengths." University of Akron / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1427827046.

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42

Liu, Jianning. "Stress Relaxation Behavior of Polymer Glasses in Both Extension and Compression." University of Akron / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1427995606.

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43

Shi, Feimo. "A THERMO- AND LIGHT- SENSITIVE STAR-LIKE COPOLYMER: DESIGN, SYNTHESIS, AND POTENTIAL APPLICATION FOR DRUG DELIVERY SYSTEM." Case Western Reserve University School of Graduate Studies / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=case1428072959.

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44

Zhong, Weijie. "The Effect of Hydrophilic Monomer in Core-shell Latex." University of Akron / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1436453067.

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45

Liu, Gengxin. "Nonlinear Rheology of Long-Chain Branched Polymers." University of Akron / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1436977058.

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46

HE, ZHOUYING. "ORGANIC/INORGANIC HYBRID COATINGS FOR ANTICORROSION." University of Akron / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1437870016.

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47

Pangilinan, Katrina Dayoan. "Layer-by-Layer and Photochemical Grafting of ATRP Initiators for Thermoresponsive Surfaces." Case Western Reserve University School of Graduate Studies / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=case1448375686.

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48

Michal, Brian. "Multi-Functional Stimuli-Responsive Polymers." Case Western Reserve University School of Graduate Studies / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=case1459440396.

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49

Sun, Jian. "Molecular Janus Particles Based On Functionalized [60]Fullerenes: Precise Synthesis And Self-Assembly Behaviors In Solution." University of Akron / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1460373051.

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50

Stilke, Morgan A. "Diffusive and Deformation Behavior of Physically Crosslinked Hydrogels." University of Akron / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1460384954.

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