Design,Synthesis, and Optical/Electronic Properties of a Series of Sphere-Rod Shape Amphiphiles Based on the C60-oligofluorene Conjugates

A series of sphere-rod shape amphiphiles were designed and synthesized by connecting the rod-like oligofluorenes with different lengths(OF_n) to the different positions of the spherical [60]fullerene(C_(60)) through a rigid linkage. The conjugates were characterized by ~1H-NMR, ~(13)C-NMR, FTIR, EA and MALDI-TOF mass spectrometry. The optical and electronic properties of the conjugates were studied by UV-Vis absorption spectroscopy, fluorescence spectrometry, and cyclic voltammetry. The results from UV-Vis absorption spectroscopy and cyclic voltammetry indicated that the energy profiles of C_(60) and OF_n remained unchanged when different lengths of OF_n were attached to C_(60). The electron affinities of the OF_n-C_(60) conjugates were close to that of C_(60), while slight electronic interaction was found between the two individual chromophores(C_(60) and OF_n) in their ground states. The fluorescence spectra exhibited a complete fluorescence quenching in the toluene solution, suggesting an effective energy transfer from OF_n to C_(60). It presents a systematic study on the selfassembly, structure-property relationship, and potential technical applications of the conjugates.     

Finite Element Analysis of Shape Memory Alloy Adaptive Trusses with Geometrical Nonlinearities

This contribution deals with the nonlinear analysis of shape memory alloy (SMA) adaptive trusses employing the finite element method. Geometrical nonlinearities are incorporated into the formulation together with a constitutive model that describes different thermomechanical behaviors of SMA. It has four macroscopic phases (three variants of martensite and an austenitic phase), and considers different material properties for austenitic and martensitic phases together with thermal expansion. An iterative numerical procedure based on the operator split technique is proposed in order to deal with the nonlinearities in the constitutive formulation. This procedure is introduced into ABAQUS as a user material routine. Numerical simulations are carried out illustrating the ability of the developed model to capture the general behavior of shape memory bars. After that, it is analyzed the behavior of some adaptive trusses built with SMA actuators subjected to different thermomechanical loadings.     

Thermo-mechanical constitutive modeling of shape memory polyurethanes using a phenomenological approach

This study examined the constitutive modeling of shape memory polyurethanes (SMPUs). SMPUs exhibit a thermo-responsive shape memory behavior, i.e., a thermally fixed temporary shape at a low temperature that returns to its original (permanent) shape when heated. This unique property arises from the molecular configuration of their hard and soft segments; the latter can form a variable state ranging from a rubbery (active) to rigid (frozen) phase according to temperature, while the former undergoes little deformation and acts as a fixed net between the soft segments. In this study, a three-phase phenomenological model (one hard segment phase and two (active and frozen) soft segment phases) was developed to describe the deformation behavior of SMPUs according to their microstructure. The stress and strain relationships of each phase are described mathematically using one three-element viscoelastic and two Mooney–Rivlin hyperelastic equations, respectively. The total stress was calculated by combining those equations via some internal variables that can track the volume fractions of the active and frozen phases and a non-mechanical frozen strain. For validation, the cyclic thermo-mechanical behavior of a SMPU was predicted. These predictions were compared with the experimental results with reasonable agreement between them.     

A constitutive theory for shape memory polymers. Part II: A linearized model for small deformations

A constitutive theory is developed for shape memory polymers. It is to describe the thermomechanical properties of such materials under large deformations. The theory is based on the idea, which is developed in the work of Liu et al. [2006. Thermomechanics of shape memory polymers: uniaxial experiments and constitutive modelling. Int. J. Plasticity 22, 279-313], that the coexisting active and frozen phases of the polymer and the transitions between them provide the underlying mechanisms for strain storage and recovery during a shape memory cycle. General constitutive functions for nonlinear thermoelastic materials are used for the active and frozen phases. Also used is an internal state variable which describes the volume fraction of the frozen phase. The material behavior of history dependence in the frozen phase is captured by using the concept of frozen reference configuration. The relation between the overall deformation and the stress is derived by integration of the constitutive equations of the coexisting phases. As a special case of the nonlinear constitutive model, a neo-Hookean type constitutive function for each phase is considered. The material behaviors in a shape memory cycle under uniaxial loading are examined. A linear constitutive model is derived from the nonlinear theory by considering small deformations. The predictions of this model are compared with experimental measurements.     

A constitutive theory for shape memory polymers. Part I: Large deformations

A constitutive theory is developed for shape memory polymers. It is to describe the thermomechanical properties of such materials under large deformations. The theory is based on the idea, which is developed in the work of Liu et al. [2006. Thermomechanics of shape memory polymers: uniaxial experiments and constitutive modeling. Int. J. Plasticity 22, 279-313], that the coexisting active and frozen phases of the polymer and the transitions between them provide the underlying mechanisms for strain storage and recovery during a shape memory cycle. General constitutive functions for nonlinear thermoelastic materials are used for the active and frozen phases. Also used is an internal state variable which describes the volume fraction of the frozen phase. The material behavior of history dependence in the frozen phase is captured by using the concept of frozen reference configuration. The relation between the overall deformation and the stress is derived by integration of the constitutive equations of the coexisting phases. As a special case of the nonlinear constitutive model, a neo-Hookean type constitutive function for each phase is considered. The material behaviors in a shape memory cycle under uniaxial loading are examined. A linear constitutive model is derived from the nonlinear theory by considering small deformations. The predictions of this model are compared with experimental measurements.     

An incremental variational approach to coupled thermo-mechanical problems in anelastic solids. Application to shape-memory alloys

We study the coupled thermo-mechanical problem that is obtained by combining generalized standard materials with Fourier’s law for heat conduction. The analysis is conducted in the framework of non-smooth mechanics in order to account for possible constraints on the state variables. This allows models of damage and phase-transformation to be included in the analysis. In view of performing numerical simulations, an incremental thermo-mechanical problem and corresponding variational principles are introduced. Conditions for existence of solutions to the incremental problem are discussed and compared with the isothermal case. The numerical implementation of the proposed approach is studied in detail. In particular, it is shown that the incremental thermo-mechanical problem can be recast as a concave maximization problem and ultimately amounts to solve a sequence of linear thermal problems and purely mechanical (i.e. at a prescribed temperature field) problems. Therefore, using the proposed approach, thermo-mechanical coupling can be implemented with low additional complexity compared to the isothermal case, while still relying on a sound mathematical framework. As an application, thermo-mechanical coupling in shape memory alloys is studied. The influence of the loading strain-rate on the phase transformation and on the overall stress–strain response is investigated, as well as the influence of the thermal boundary conditions. The numerical results obtained by the proposed approach are compared with numerical and experimental results from the literature.     

On small homotopies of loops

Two natural questions are answered in the negative:

• “If a space has the property that small nulhomotopic loops bound small nulhomotopies, then are loops which are limits of nulhomotopic loops themselves nulhomotopic?”

• “Can adding arcs to a space cause an essential curve to become nulhomotopic?”

The answer to the first question clarifies the relationship between the notions of a space being homotopically Hausdorff and π₁-shape injective.

Mechanical properties and deformation morphologies of covalently bridged multi-walled carbon nanotubes: Multiscale modeling

We formulate a multiscale modeling framework to investigate the deformation morphologies and energetics of covalently bridged multi-walled carbon nanotubes (MWCNTs). The formulation involves extending a previously established quasi-continuum model by incorporating the inter-wall bridging energy density function into the constitutive relations via message passing from fully atomistic simulations. Using the extended numerical model, we studied the mechanical responses of the 10-walled MWCNT with varying inter-wall bridge densities under torsion, bending, and uniaxial compression. Our simulation results show that the presence of inter-wall covalent bridges not only enhances the post-buckling rigidities of the MWCNTs, but also modifies the deformation morphologies and morphology pathways. For bending and uniaxial compression, we constructed in the space of bridge density and applied strain the deformation morphology phase diagram, where three phases, uniformly deformed phase, rippling pattern, and diamond-shaped pattern, are identified and separated by linear phase boundaries. We attribute the deformation phase transitions to the interplay of inter-wall and intra-wall interaction energies. The multiple shape transitions of MWCNTs and the elastic nature of the deformation suggest that MWCNTs can be designed as shape-memory nanodevices with tunable stabilities.     

Barlow-wu continuum systems: A discussion on the model

Barlow-Wu continuum structure functions have been introduced in the past as one particularly interesting family of continuum structure functions. In this paper we provide an alternative characterization for such continuum structure functions, showing other interesting properties. Research supported by Dirección General de Investigación Científica y Técnica (DGICYT), national grants number PB91-0389 and number BE91-225.