Plasma surface functionalization of poly[bis(2,2,2-trifluoroethoxy)phosphazene] films and nanofibers

Polyphosphazenes are a class of hybrid organic-inorganic macromolecules with high thermo-oxidative stability and good solubility in many solvents. Fluoroalkoxy phosphazene polymers also have high surface hydrophobicity. A method is described to tune this surface property while maintaining the advantageous bulk materials characteristics. The polyphosphazene single-substituent polymer, poly[bis(2,2,2-trifluoroethoxy)phosphazene], with flat film, fiber mat, or bead mat morphology was surface functionalized using an atmospheric plasma treatment with oxygen, nitrogen, methane, or tetrafluoromethane/hydrogen gases. Surface chemistry changes were detected by static water contact angle (WCA) measurements as well as X-ray photon spectroscopy (XPS). It was found that changes in the WCA of as much as 150 degrees occurred, accompanied by shifts in the ratio of elements on the polymer surface as detected by XPS. Overall this plasma technique provides a convenient method for the generation of specific surface characteristics while maintaining the hydrophobicity of the bulk material.     

Orthotropic strain rate potential for the description of anisotropy in tension and compression of metals

In this paper, a macroscopic anisotropic strain rate potential, which can describe both the anisotropy and tension-compression asymmetry of the plastic response of textured metals is derived. This strain rate potential is the exact work-conjugate of the anisotropic stress potential CPB06 of Cazacu et al. (2006). Application of the developed strain rate potential to HCP high-purity alpha-titanium is presented.     

On the existence of indeterminate solutions to the equations of motion under non-associated flow

Under certain conditions, an indeterminate solution exists to the equations of motion for dynamic elastic–plastic deformation of materials using constitutive laws based on non-associated flow that suggests that an initially unbounded dynamic perturbation in the stress can develop from a quiescent state on the yield surface. The existence of this indeterminate solution has been alleged to discourage use of non-associated flow rules for both dynamic and quasi-static analysis theoretically. It is shown in this paper that the indeterminate solution that may solve the equations of motion is intrinsically dynamic, and it determinately goes to zero in the quasi-static limit regardless of other indeterminate parameters. Consequently, the existence of this unstable dynamic solution has no impact on stability and use of non-associated flow rules for analysis of the quasi-static problem. More importantly, for dynamic applications, it is also shown that the indeterminate solution solves the equations of motion only if critical restrictions are applied to the constitutive equations such that the effective modulus during loading is constant and the direction of the perturbation is unidirectional over a finite time interval. It is shown that common components of the constitutive laws used in metal forming and deformation analysis are inconsistent with these restrictions. So, these common models can be generalized to include non-associated flow for analysis of the dynamic problem without concern that the solution will become indeterminate.     

Hysteresis loops predicted by isoenergy density theory for polycrystals. Part I: fundamentals of non-equilibrium thermal–mechanical coupling effects

When a polycrystal is stressed or strained at fifty percent of the corresponding yield value, damage will be inflicted non-homogeneously in the material due to the fact that the stress and/or strain distribution is non-uniform even if isotropy and homogeneity are assumed for the initial microstructure. This effect will be cumulated for each cycle of the load if the applied stress or strain is repeated continuously. Nucleation of microcracks can eventually lead to the propagation of a macrocrack.The process of damage accumulation in fatigue is defined to be sufficiently slow such that inhomogeneity of material behavior created by loading is a significant factor that can not be arbitrarily dismissed without a good reason. What this means specifically is that the difference of the stress and strain behavior at each point in a fatigue specimen must be accounted for in the analytical model in order to predict the correct cumulative effect. Such a requirement translates into a non-equilibrium formulation where the constitutive relations for each point and loading cycle must be determined separately. In this sense, the true problem of fatigue cannot be completely treated by the classical continuum mechanics approach that is limited to equilibrium mechanics for a closed system. Having said this, the isoenergy density theory will be applied to estimate the hysteresis loops of a hour-glass profile cylindrical bar specimen as recommended by the American Society for Testing and Materials (ASTM) for low-cycle fatigue.The work will be divided into two parts. Part I will cover the fundamentals of a non-equilibrium theory where the continuum elements are finite in size; they do not vanish in the limit. Therefore, size effects are immediately encountered as a function of time. General expressions for the rate change of volume of these elements with surface area are derived such that they can be computed from the nine displacement gradients. These elements can differ in size and must fit together without discontinuities or gaps to form the continuum. The condition of isoenergy energy density is invoked such that the size of these individual elements under large and finite deformation and rotation can be determined without loss in generality. The existence of such a space having the property of the same isoenergy density in all directions is thus proved. This enables the establishment of the one dimensional energy state with that in three dimensions without restriction, the absence of which has prevented the development of a complete non-linear theory of mechanics that can be solved in a direct fashion in contrast to the inverse method of assuming the displacement field. Illustration is provided for deriving the constitutive relation incrementally for a given location for the hour-glass specimen made of 6061-T6 aluminum. Once the specimen is loaded, each material point will follow a different stress and strain curve according to the local displacement rate. Hence, the method applies to material with non-homogeneous microstructure if their individual expressions can be assessed and fed into the computer.Part II computes for the non-equilibrium temperature and an entropy-like quantity that can be positive and negative. This implies that the system can absorb or dissipate energy with reference to the surrounding. Additional data for hysteresis loops are given for 6061-T6 aluminum, SAE 4340 steel and Ti–8Al–1Mo–1V titanium. Accumulation of the local hysteresis energy per cycle is found to be the highest near the surface of the uniaxial specimen where load symmetry prevails. This is a consequence of the difference in accumulation of the energy density due to distortion in contrast to dilatation at the specimen center. This is why fatigue cracks tend to nucleate near the specimen surface, at a small distance towards the interior. Another distinct feature of fatigue is that the non-equilibrium temperature is found to oscillate about the ambient temperature while the local stress states fluctuate between tension and compression. This temperature reversal behavior is typical of non-equilibrium behavior and also occurs under monotonic loading. The space and time variations of the dissipated energy density for different materials are found to be related to the initial monotonic energy density or area under the true stress and true strain curve.What will be demonstrated is that no special consideration need to be made when applying the isoenergy density theory for analyzing the nucleation of micro and macrocracks in addition to failure of the specimen. Crack nucleation under fatigue is assumed to occur when the total hysteresis energy reaches a critical value. It is possible to establish a relation between the average hysteresis energy per cycle and the number of cycles to failure. The proposed method requires only a knowledge of the initial monotonic energy density curve for a given material. Predicted results for the fatigue of cylindrical bar specimens with hour-glass profile are given and they can be found in Part II of this work.     

Band structure of118Xe

High spin states of¹¹⁸Xe have been investigated by means of γ ray spectroscopy using the⁹²Mo(²⁹Si,2pn) at a bombarding energy of 110 MeV. Several new side bands as well as the yrast band were established. A band crossing between the ground state and super bands was observed at ?ω_c = 0.39 MeV. A negative parity band with two quasi particle excitation, and a quasi γ band were also identified.