Abnormal brittle-ductile transition for glassy polymers after free and constrained melt stretching: The role of molecular alignment

Polymer ◽  
2021 ◽  
pp. 124199
Author(s):  
Qi Yan ◽  
Tingyu Xu ◽  
Wenwen Zhang ◽  
Changzhu Lv ◽  
Hang Guo ◽  
...  
2019 ◽  
Vol 116 (28) ◽  
pp. 13862-13866 ◽  
Author(s):  
Kun Cao ◽  
Richard van Lent ◽  
Aart W. Kleyn ◽  
Mitsunori Kurahashi ◽  
Ludo B. F. Juurlink

Low coordinated sites on catalytic surfaces often enhance reactivity, but the underlying dynamical processes are poorly understood. Using two independent approaches, we investigate the reactivity of O2impinging onto platinum and resolve how step edges on (111) terraces enhance sticking. At low incident energy, the linear dependence on step density, independence of step type, and insensitivity to O2’s molecular alignment show that trapping into a physisorbed state precedes molecular chemisorption and dissociation. At higher impact energies, direct molecular chemisorption occurs in parallel on steps and terraces. While terraces are insensitive to alignment of the molecule within the (111) plane, steps favor molecules impacting with their internuclear axis parallel to the edge. Stereodynamical filtering thus controls sticking and dissociation of O2on Pt with a twofold role of steps.


2020 ◽  
Vol 55 (2) ◽  
pp. 145-158
Author(s):  
A. J. Hill ◽  
A. W. Thornton ◽  
R. H. J. Hannink ◽  
J. D. Moon ◽  
B. D. Freeman

2020 ◽  
Author(s):  
Massimo Calcara

<p>The Dilatancy Diffusion model of Scholz et al (1973) is a model describing saturated rocks behaviour under differential tectonic stress in time domain, and one of the first trial of earthquake precursory phenomena listing and explanation. After around 50 years, improvements, outline and structure of this however successful model are still a reference point of many researcher. The role of water has been explained only as a pressure transducer, acting on host rocks, during the various stages of dilatancy diffusion, acting as a pressure cycle.</p><p>Theme of present model is the water active chemical role in DD.</p><p>A temperature pressure diagram of water aggregation state could be drawn as a section of the earth crust. Assuming that the brittle ductile transition line could be localised even close to 500 °C isotherm, most hypocentre are surely localised in liquid phase area, while some main shock localisation may fall even in water supercritical region.</p><p>I modelled the water isothermal behaviour in relation of most relevant variable acting on water in dilatancy diffusion: pressure. Pressure acting on water could drop drastically as soon as microcraks open. Then, water flow into newly created fractures, and, since tectonic load continues, pressure rise again, before main shock. In this pressure cycle, water chemical response, could be splitted into two diverse fields: liquid and supercritical, resulting however in a rock weakening.</p><ul><li>1) <strong>Liquid</strong>. The entity of depressurisation makes the difference. According to Scholz et al (1973), and Brace et al (1966), the entity is high. It is a matter of water quantities and of volumetric geometry of microcracks. Ionic solubility depends slightly from pressure. Going into vapour phase is equal to a distillation process: when pressures rise again, this kind of water is extremely aggressive toward newly opened rock surfaces. If not, water could maintain most, not all, solute in. In every case, molecules like CO<sub>2</sub> and H<sub>2</sub> migrates away from water and, thanks to their characteristics (radius and electrostatic field), following the path of extremely little fissurations, normally secluded to water. Resulting water changes its chemical content.</li> <li>2) <strong>Supercritical.</strong> Molecular structure of this aggregation state makes this fluid compressible. That is, its density varies highly with pressure. Solvent capability varies highly with density: supercritical water acquires polar solvent power with growing density. Solubility depends highly from pressure, with all consequences.</li> </ul><p><strong>Subcritical crack growth</strong>. It is a common point of 1) and 2), and it could be a function of dissociation grade of water too. In an environment, with freshly created surfaces, quartz and silicates are subjected to a further weakening due to high dissociated water.</p><p>The integration of water chemistry in dilatation diffusion model is a needed upgrade and depict a situation in which, as soon as new crack creates, the chemical action of water can trigger a near irreversible process of rock weakening accelerating the main shock, since rock resistance could be lowered well below original breaking load.</p>


2018 ◽  
Vol 26 (24) ◽  
pp. 32225
Author(s):  
Shilin Hu ◽  
Zheng Shu ◽  
Mingqing Liu ◽  
Li Guo ◽  
Xiaolei Hao ◽  
...  

Polymers ◽  
2020 ◽  
Vol 12 (4) ◽  
pp. 769
Author(s):  
Leno Mascia ◽  
Yannis Kouparitsas ◽  
Davide Nocita ◽  
Xujin Bao

Antiplasticization of glassy polymers, arising from the addition of small amounts of plasticizer, was examined to highlight the developments that have taken place over the last few decades, aiming to fill gaps of knowledge in the large number of disjointed publications. The analysis includes the role of polymer/plasticizer molecular interactions and the conditions leading to the cross-over from antiplasticization to plasticization. This was based on molecular dynamics considerations of thermal transitions and related relaxation spectra, alongside the deviation of free volumes from the additivity rule. Useful insights were gained from an analysis of data on molecular glasses, including the implications of the glass fragility concept. The effects of molecular packing resulting from antiplasticization are also discussed in the context of physical ageing. These include considerations on the effects on mechanical properties and diffusion-controlled behaviour. Some peculiar features of antiplasticization regarding changes in Tg were probed and the effects of water were examined, both as a single component and in combination with other plasticizers to illustrate the role of intermolecular forces. The analysis has also brought to light the shortcomings of existing theories for disregarding the dual cross-over from antiplasticization to plasticization with respect to modulus variation with temperature and for not addressing failure related properties, such as yielding, crazing and fracture toughness.


1993 ◽  
Vol 12 (1) ◽  
pp. 65-78 ◽  
Author(s):  
N. Mohammadi ◽  
R. Bagheri ◽  
G.A. Miller ◽  
A. Klein ◽  
L.H. Sperling

2011 ◽  
Vol 184 (3-4) ◽  
pp. 160-171 ◽  
Author(s):  
C. Doglioni ◽  
S. Barba ◽  
E. Carminati ◽  
F. Riguzzi

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