ABSTRACT
The underlying microscopic response of filler networks in reinforced rubber to dynamic strain is not well understood due to the experimental difficulty of directly measuring filler network behavior in samples undergoing dynamic strain. This difficulty can be overcome with in situ X-ray photon correlation spectroscopy (XPCS) measurements. The contrast between the silica filler and the rubber matrix for X-ray scattering allows us to isolate the filler network behavior from the overall response of the rubber. This in situ XPCS technique probes the microscopic breakdown and reforming of the filler network structure, which are responsible for the nonlinear dependence of modulus on strain, known in the rubber science community as the Payne effect. These microscopic changes in the filler network structure have consequences for the macroscopic material performance, especially for the fuel efficiency of tire tread compounds. Here, we elucidate the behavior with in situ dynamic strain XPCS experiments on industrially relevant, vulcanized rubbers filled (13 vol %) with novel air-milled silica of ultrahigh-surface area (UHSA) (250 m2/g). The addition of a silane coupling agent to rubber containing this silica causes an unexpected and counterintuitive increase in the Payne effect and decrease in energy dissipation. For this rubber, we observe a nearly two-fold enhancement of the storage modulus and virtually equivalent loss tangent compared to a rubber containing a coupling agent and conventional silica. Interpretation of our in situ XPCS results simultaneously with interpretation of traditional dynamic mechanical analysis (DMA) strain sweep experiments reveals that the debonding or yielding of bridged bound rubber layers is key to understanding the behavior of rubber formulations containing the silane coupling agent and high-surface area silica. These results demonstrate that the combination of XPCS and DMA is a powerful method for unraveling the microscale filler response to strain which dictates the dynamic mechanical properties of reinforced soft matter composites. With this combination of techniques, we have elucidated the great promise of UHSA silica when used in concert with a silane coupling agent in filled rubber. Such composites simultaneously exhibit large moduli and low hysteresis under dynamic strain.
ABSTRACT
Filled rubber materials are key in many technologies having a broad impact on the economy and sustainability, the most obvious being tire technology. Adding filler dramatically improves the strength of rubber by reinforcement and tailoring the type of filler, and the chemistry of the interface between the filler and rubber matrix is important for optimizing performance metrics such as fuel efficiency. In a highly loaded, silica-filled, cross-linked model rubber closely mimicking commercial materials, both the filler network structure and the dynamics of the silica filler particles change when the silica surface is modified with silane coupling agents. Reduction in size scales characteristic of the structure is quantified using ultra-small-angle X-ray scattering (USAXS) measurements and the particle dynamics probed with X-ray photon correlation spectroscopy (XPCS). While the structure averaged over the scattering volume changes little with aging after step strain, the dynamics slow appreciably in a manner that varies with the treatment of the silica filler. The evolution of filler particle dynamics depends on the chemical functionality at the silica surface, and observing these differences suggests a way of thinking about the origins of hysteresis in nanoparticle-reinforced rubbers. These microscopic filler dynamics are correlated with the macroscopic stress relaxation of the filled materials. The combination of static and dynamic X-ray scattering techniques with rheological measurements is a powerful approach for elucidating the microscopic mechanisms of rubber reinforcement.
ABSTRACT
Se estudiaron prospectivamente a 100 pacientes con diagnóstico clínico de cirrosis hepática. Realizándoles endoscopia del tubo digestivo proximal y rastreo ultrasonográfico de la venas porta y esplénica, bazo y características del hígado. Existió una correlación significativa entre la medida del tronco de la porta, diámetro mayor del bazo y el tamaño endoscópico de las várices esofágicas. Se concluye que la ultrasonografía de tiempo real, es un método útil para investigar signos de hipertensión portal; en centros hospitalarios donde se cuenta con ayuda endoscópica, infiriendo que al determinar éstos, puede especularse la presencia de signos endoscópicos de hipertensión portal, precisando la necesidad de endoscopía proximal
