Academic literature on the topic 'Viscoelasticity. Polymers. Polymerization'

ABSTRACT Bulk viscoelasticity and tensile behavior are examined for cross-linked compounds made of mussel-mimetic elastomers of varied functionality design. During polymerization, the mussel-mimetic functionalities containing the 3,4-dihydroxyphenyl (or catechol) group can be incorporated at the molecule chain head, along the backbone, and/or at the molecule chain tail. The compounds are either unfilled or filled to the same filler volume fraction with a single filler chosen among carbon black (hydrophobic), precipitated silica (hydrophilic), and titanium oxide (hydrophilic). For polymers bearing multiple mussel-mimetic functional groups, the polymer cold flow resistance becomes significantly enhanced, arising from the strong intermolecular hydrogen bonding interactions. Such strong intermolecular hydrogen-bonding interactions also affect the bulk viscoelasticity and tensile behavior for the cross-linked gum compounds. Because the mussel-mimetic functional groups exhibit obvious affinity to all three types of filler particles, the extent of modification to bulk viscoelasticity and reinforcement for the filled compounds is observed to vary with the distribution of such functionalities along a polymer molecule, the chemical groups immediately next to the catechol group, and the specific type of filler. As expected, microscale filler dispersion is improved from the strong polymer–filler interactions.

A quaternary polymer (HGP) was prepared by the free-radical polymerization of acrylamide, acrylic acid, maleic anhydride functionalized β-cyclodextrin (MAH-β-CD), and N-(3-methacrylamidopropyl)-N, N-dimethylnaphthalen-1-aminium chloride (NAP). It was found that host–guest behavior occurred most effectively at a molar rate of NAP and CD with 1:1, which exhibited better solubility than hydrophobically associative polymer. Moreover, the as-prepared polymer has superior salt tolerance, shear resistance, and viscoelasticity due to host–guest strategy. More importantly, the HGP solution simulates the distribution of formation water in the Bohai SZ1-1 oilfield has good rheological properties at 120 °C. All results show that the proposed polymer could be a competitive candidate in oilfield applications such as fracturing fluids, displacement fluids, and drilling fluids.

A novel cationic surfmer, methacryloxyethyl-dimethyl cetyl ammonium chloride (DMDCC), is synthesized. The micellar properties, including critical micelle concentration and aggregation number, of DMDCC-SDS mixed micelle system are studied using conductivity measurement and a steady-state fluorescence technique. A series of water-soluble associative copolymers with acrylamide and DMDCC are prepared using the mixed micellar polymerization. Compared to conventional micellar polymerization, this new method could not only reasonably adjust the length of the hydrophobic microblock, that is,NH, but also sharply reduce the amount of surfactant. Their rheological properties related to hydrophobic microblock and stickers are studied by the combination of steady flow and linear viscoelasticity experiments. The results indicate that both the hydrophobic content and, especially the length of the hydrophobic microblock are the dominating factors effecting the intermolecular hydrophobic association. The presence of salt influences the dynamics of copolymers, resulting in the variation of solution characters. Viscosity measurement indicates that mixed micelles between the copolymer chain and SDS molecules serving as junction bridges for transitional network remarkably enhance the viscosity. Moreover, the microscopic structures of copolymers at different experimental conditions are conducted by ESEM. This method gives us an insight into the preparation of hydrophobically associative water-soluble copolymers by cationic surfmer-anionic surfactant mixed micellar polymerization with good performance.

Polymerization and depolymerization of cytoskeletal elements maintaining cytoplasmic stiffness are key factors in the control of cell crawling. Rheometry is a significant tool in determining the mechanical properties of the single elements in vitro. Viscoelasticity of gels formed by these polymers strongly depends on both the length and the associations of the filaments (e.g. entanglements, annealings and side-by-side associations). Ultrasound attenuation is related to viscosity, sound velocity and supramolecular structures in the sample. In combination with a small glass fibre (2mm×50µm), serving as a viscosity sensor, an acoustic microscope was used to measure the elasticity and acoustic attenuation of actin solutions. Changes in acoustic attenuation of polymerizing actin by far exceed the values expected from calculations based on changes in viscosity and sound velocity. During the lag-phase of actin polymerization, attenuation slightly decreases, depending on actin concentration. After the half-maximum viscosity is accomplished and elasticity turns into steady state, attenuation distinctly rises. Changes in ultrasound attenuation depend on actin concentration, and they are modulated by the addition of α-actinin, cytochalasin D and profilin. Thus absorption and scattering of sound on the polymerization of actin is related to the packing density of the actin net, entanglements and the length of the actin filaments. Shortening of actin filaments by cytochalasin D was also confirmed by electron micrographs and falling-ball viscosimetry. In addition to viscosity and elasticity, the attenuation of sound proved to be a valuable parameter in characterizing actin polymerization and the supramolecular associations of F-actin.

Abstract The paper gives a brief survey of the state of friction and abrasion research with a view of the possibility to use laboratory methods for the development of new compounds with optimal traction and abrasion properties. It shows that viscoelasticity plays a decisive role in friction and in this way measurements of the dynamic properties give a good indication of the possibilities for good traction properties. However, friction is still a good deal more complex than the modulus or loss factor curves. It takes in different frequency ranges and temperatures in the contact area so that a direct laboratory measurement of these properties is still very desirable. If the speed and temperature correspond to the log aTv values experienced in practice and the laboratory track structure and texture is not too far removed from that of road surfaces, the correlation with road tests is high. To simulate the structure and texture of road surfaces with durable laboratory surfaces, a combination of two surfaces may be necessary. Abrasion is not only influenced by the strength properties of the rubber but also by oxidation and thermal degradation. To give these processes the correct weight in the laboratory, the testing conditions have to be mild and a combination of several conditions is necessary in order to demonstrate the complexity of interactions, which can lead to ranking reversals. Energy dissipation, speed, and abrasive surface structure and texture are identified as prime variables to achieve a high correlation with road wear. Since viscoelasticity, encompassing not only polymer but also filler, oil-extension, curing and other compound additives, plays a major role in both friction and wear, the rolling resistance of the compound is always effected and has to be taken into account. Modern polymerization methods and new filler concepts make it possible to change the viscoelastic properties in such detail that high friction and—to the degree to which strength contributes to wear—high wear resistance can be combined with low rolling resistance. This development has certainly not reached its climax yet. Exciting times lie ahead for tire compounders, polymer- and filler chemists alike.

In this work, high-performance thermoplastic polyurethane elastomer/carbon dots (TPU/CDs) bulk nanocomposites with strong luminescence were fabricated via in situ polymerization. The CDs were synthesized from citric acid and 2-aminothiophenol. Transmission electron microscope, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and systematic characterization indicated the formation of the CDs and the covalent conjugation of the CDs with TPU. The optical properties of the TPU/CDs nanocomposites were characterized by ultraviolet–visible and fluorescence spectroscopy. Compared to the initial solid-state CDs (the absolute photoluminescence quantum yields (QY): 20%), all the composites exhibited stronger luminescence behavior. When the CDs content was 0.5 wt%, the QY was as high as 68%. Furthermore, the rheological, mechanical, and thermal properties of the nanocomposites were investigated. The rheological properties established the structure–property relationships of the composites. The incorporation of the CDs enhanced the elastic response in viscoelasticity of the nanocomposites. The tensile strength of 1.0 wt% CDs loaded TPU increased from 18.2 MPa to 28.6 MPa, nearly 57% higher than that of the neat TPU. Given the excellent Ag+ detection performance of the CDs, the high QY and the processability of the nanocomposites, Ag+ detection experiments for the composite film were performed. The study will facilitate the applications of luminescent nanocomposites in potential fields.

Tato dizertační práce se zabývá studiem morfogeneze dimethakrylátových sítí. V práci byly využity zjednodušené systémy založené na monomerech, které bývají typicky využívány jako složky matric pryskyřičných kompozitních materiálů využívaných v oblasti záchovné stomatologie. Kinetika a mechanismy formování polymerních sítí byly studovány především s ohledem na strukturu jednotlivých monomerů, jejich vzájemný molární poměr a koncentraci iniciačního systému využitého pro radikálovou polymeraci. Vypočtené profily konverze funkčních skupin a reakčních rychlostí byly využity jako základ pro pochopení a interpretaci mechanismů morfogeneze sítí a porovnání se známými modely. Dále byla studována kinetika termické degradace, která je s morfologií vytvrzených sítí přímo spjata. V rámci takto charakterizovaných systémů byla stanovena teplotní závislost dynamického modulu a byl popsán vztah mezi supra-molekulární strukturou dimethakrylátových sítí a jejich viskoelastickou odezvou v daném teplotním rozmezí. Kinetika polymerace byla studována pomocí diferenční kompenzační foto-kalorimetrie (DPC) a infračervené spektroskopie (FTIR). Proces termické degradace byl analyzován pomocí termo-gravimetrické analýzy (TGA). Viskoelastické parametry byly charakterizovány pomocí dynamicko-mechanické analýzy (DMA). Reaktivita jednotlivých systémů je přímo odvozena od molekulární struktury monomerů, která ovlivňuje mobilitu reagujících složek v průběhu polymerace. Kinetika polymerace je řízena především difúzí, přičemž její rychlost je dána tuhostí monomerní páteře, koncentrací funkčních skupin a vlivem fyzikálních interakcí. Omezená mobilita rostoucích řetězců, postranních funkčních skupin i samotných monomerů vede k monomolekulární terminaci makro-radikálů a omezení stupně konverze funkčních skupin. Vzhledem k tomu, že k zásadnímu omezení mobility dochází již v počáteční fázi polymerace, tj. v bodu gelace, je případná termodynamická nestabilita vedoucí k fázové separaci polymerujícího systému potlačena a proces kopolymerace je ve své podstatě náhodný. To bylo prokázáno i prostřednictvím identifikace jedné teploty skelného přechodu u charakterizovaných kopolymerů. Heterogenní charakter morfogeneze je spjat s rozdílnou reaktivitou postranních funkčních skupin. V počátečních fázích polymerace dochází k propagaci reakcí postranní funkční skupiny s radikálem na stejném rostoucím řetězci, což vede ke vzniku tzv. primárního cyklu. Pravděpodobnost cyklizace souvisí především s flexibilitou monomerní páteře. Heterogenita polymerace je charakterizována vznikem vnitřně zesítěných struktur, tzv. mikrogelů, a jejich následným spojováním. Tuhost monomeru naopak přispívá k vyšší efektivitě zesítění a více homogenní morfologii vytvrzené sítě. Heterogenita dimethakrylátových sítí se odráží v mechanismu termické degradace, přičemž přítomnost strukturně odlišných domén vede k rozkladu ve dvou krocích. Průběh soufázového modulu a teplota skelného přechodu korelují s tuhostí polymerních sítí, efektivitou zesítění a přítomností fyzikálních interakcí, které vyztužují strukturu sítě nad rámec kovalentního zesítění. Heterogenní morfologie sítí se projevuje rozšiřováním spektra relaxačních časů. Experimentální data jsou v kvalitativní shodě s existujícími numerickými modely popisujícími kinetiku radikálové polymerace multifunkčních monomerů.

L’objectif principal de ce travail de thèse est de synthétiser par polymérisation RAFT en milieux homogène et hétérogène des copolymères à blocs amphiphiles de structure bien contrôlée. Un procédé simplifié, « ont pot » a donc été développé pour synthétiser ces copolymères et les auto-assembler en particules dans l’eau. Cette méthode dite de « l’auto-assemblage induit par la polymérisation » (PISA) permet de synthétiser en quantité des copolymères à blocs amphiphiles en milieux aqueux sans aucune étape de purification intermédiaire. Dans ce procédé, deux étapes successives sont effectuées dans le même réacteur. La 1ère étape a pour but de synthétiser des agents RAFT macromoléculaires hydrophiles (macroRAFTs) par polymérisation en solution dans l’eau. Ces macroRAFTs fonctionnalisés par un groupement trithiocarbonate sont ensuite utilisés dans le même réacteur comme agents de contrôle etprécurseurs de stabilisants pour la polymérisation en émulsion du monomère hydrophobe directement dans l’eau. Lors de cette 2nde étape, des copolymères à blocs amphiphiles sont formés et s’auto-assemblent sous forme de particules aux morphologies variées (sphères, filaments et vésicules). Nous avons alors étudiés les différents paramètres (pH, température de polymérisation en émulsion, nature des monomères hydrophobe et hydrophile, taux de solide, masses molaires des blocs hydrophobe et hydrophile, etc)gouvernant la formation de morphologies spécifiques. Un objectif supplémentaire a été l’étude du comportement viscoélastique linéaire des suspensions de ces nano-fibres polymère à une température inférieure (25°C) ou supérieure (130°C) à la température de transition vitreuse (Tg) du coeur polystyrène des nano-fibres. A T < Tg, les nano-fibres sont parfaitement rigides et obéissent à une dynamique brownienne de bâtonnets. En effet, les lois d’échelles déduites du comportement viscoélastique de ces suspensions obéissent aux lois prédites par Doi-Edwards. En revanche, ces nano-fibres sont flexibles pour T > Tg et ont une dynamique Brownienne de chaînes polymères en solution
The aim of this work was synthesis of well-defined amphiphilic block copolymers in homogenous and heterogenous media using RAFT polymerization (Reversible Addition-Fragmentation Chain Transfer) and to study their self-assemblies in water. A one-pot process in water was developed for the synthesis of amphiphilic block copolymers that simultaneously to their growth self-assembled into nano-particles. This method called “polymerization-induced self-assembly” (PISA) allows the synthesis of large quantities of amphiphilic block copolymers in aqueous media without any intermediate purification step. During this process, two successive polymerization steps are performed in the same reactor. The first step consists in the synthesis of the hydrophilic macromolecular RAFT agents (macroRAFT agents) possessing a trithiocarbonate reactive group via RAFT in water. Without purification, these macroRAFT agents are reactivated for the polymerization of a hydrophobic monomer in the same reactor via RAFT emulsion polymerization. The resulting amphiphilic block copolymers self-assembled into nano-objects with various morphologies (spherical micelles, nanofibers and vesicles). Different parameters (pH, temperature, natureof hydrophilic and hydrophobic monomers, solids contents, molar masse of hydrophilic and hydrophobic blocks, etc) control these morphologies. Besides, the viscoelastic properties of polymeric nanofibers suspensions were studied as a function of the temperature. Below the Tg of polystyrene core at 25°C, the scaling law from viscoelastic behavior of these nanofiber suspensions the Doi−Edwards theory on the Brownian dynamics of rigid rods. Above Tg at 130°C, the nanofibers are flexible and it observed that their dynamics obey the power laws for polymer chains in solution