Mechanical Anisotropy in Crystalline Saccharin: Nanoindentation Studies

The nanoindentation technique has been employed to relate the mechanical properties of saccharin single crystals with their internal structure. Indentations were performed on (100) and (011) faces to assess the mechanical anisotropy. The load-displacement (P-h) curves indicate significant differences in the nature of the plastic deformation on the two faces. The P-h curves obtained on the (011) plane are smooth, reflecting homogeneous plasticity. However, displacement bursts (pop-ins) are observed in the P-h curves obtained on the (100) plane suggesting a discrete deformation mechanism. Marginal differences exist in the hardness and modulus on the two faces that may, in part, be rationalized, although one notes that saccharin has a largely three-dimensional close-packed structure. The structural origins of the fundamentally different deformation mechanisms on (100) and (011) are discussed in terms of the dimensionality of the hydrogen bonding networks. Down the (100) planes, the saccharin dimers are stacked and are stabilized by nonspecific van der Wants interactions mostly between aromatic rings. However, down the (011) planes, the molecules are stabilized by more directional and cross-linked C-H ... O hydrogen bonds. This anisotropy in crystal packing and interactions is reflected in the mechanical behavior on these faces. The displacements associated with the pop-ins were found to he integral multiples oldie molecule separation distances. Nanoindentation offers an opportunity to compare experimentally, and in a quantitative way, the various intermolecular interactions that fire present in a molecular crystal.

Influence of cross-correlation between dipolar and chemical shift anisotropy relaxation mechanisms upon the transverse relaxation rates of 15N in macromolecules

Heteronuclear multiple-quantum coherence relaxation rate are calculated for the individual transitions of the S spin in an AIS nuclear spin system assuming that the heteronucleus (S spin) has relaxation contributions from both intramolecular dipole-dipole and chemical shift anisotropy relaxation. The individual multiplet components of the heteronuclear zero- and double-quantum coherences are shown to have different transverse relaxation rates. The cross-correlation between the two relaxation mechanisms is shown to be the dominant cause of the calculated differential line broadening. Experimental data are presented using as an example a uniformly 15N labelled sample of human epidermal growth factor.

Role of Surface Texture, Roughness, and Hardness on Friction During Unidirectional Sliding

In the present investigation, experiments were conducted by unidirectional sliding of pins made of FCC metals (Pb, Al, and Cu) with significantly different hardness values against the steel plates of various surface textures and roughness using an inclined pin-on-plate sliding apparatus in ambient conditions under both the dry and lubricated conditions. For a given material pair, it was observed that transfer layer formation and the coefficient of friction along with its two components, namely adhesion and plowing, are controlled by the surface texture of the harder mating surfaces and are less dependent of surface roughness (R (a)) of the harder mating surfaces. The effect of surface texture on the friction was attributed to the variation of the plowing component of friction for different surfaces. It was also observed that the variation of plowing friction as a function of hardness depends on surface textures. More specifically, the plowing friction varies with hardness of the soft materials for a given type of surface texture and it is independent of hardness of soft materials for other type of surface texture. These variations could be attributed to the extent of plane strain conditions taking place at the asperity level during sliding. It was also observed that among the surface roughness parameters, the mean slope of the profile, Delta (a), correlated best with the friction. Furthermore, dimensionless quantifiable roughness parameters were formulated to describe the degree of plowing taking place at the asperity level.

Enhancement of uniaxial magnetic anisotropy in Fe thin films grown on GaAs(001) with an MgO underlayer

The understanding and control of anisotropy in Fe films grown on cubic systems such as GaAs and MgO has been of interest from the point of view of applications in devices. We report magnetic anisotropy studies on Fe/GaAs(001) and Fe/MgO/GaAs(001) prepared by pulsed laser deposition. In Fe/GaAs(001), magneto optical Kerr effect (MOKE) measurements revealed a dominant uniaxial anisotropy for Fe thickness less than 20 monolayers (ML) and this was confirmed by ferromagnetic resonance (FMR) studies. Multiple steps in the hysteresis loops were observed for Fe films of thickness 20 and 25 ML. Whereas, in Fe/MgO/GaAs(001), even at 25 ML of Fe, the uniaxial anisotropy remained dominant. The anisotropy constants obtained from FMR spectra have shown that the relative strength of uniaxial anisotropy is higher as compared to the cubic anisotropy constant in the case of Fe/MgO/GaAs(001). (C) 2011 American Institute of Physics. doi:10.1063/1.3556941]

Magnetism in MnPSe3: a layered 3d(5) antiferromagnet with unusually large XY anisotropy

The anisotropic magnetic susceptibilities of single crystals of the isostructural layered antiferromagnets, MnPS3 (T-N = 78 K) and MnPSe3 (T-N = 74 K), have been measured as functions of temperature. In both compounds, divalent manganese is present in the high-spin S = 5/2 state. The anisotropies in the susceptibilities of the two are, however, very different; while the susceptibility of MnPS3 is isotropic, that of MnPSe3 shows a large XY anisotropy, unusual for a manganese compound. The anisotropic susceptibilities are described by the zero-field spin Hamiltonian: H = DSiz2 - Sigma J(ij).(S) over right arrow (S) over right arrow(j) with the quadratic single-ion anisotropy term introducing anisotropy in an otherwise isotropic situation. The exchange J and the single-ion zero-field-splitting (ZFS) parameter D were evaluated using the correlated effective-field theory of Lines. For MnPSe3, J/k = -5.29 K and D/k = 26.6 K, while for isotropic MnPS3, J/k = -8.1 K. It is suggested that the large value of the ZFS parameter for MnPSe3 as compared to MnPS3 could be due to the large ligand spin-orbit contribution of the heavier selenium.

Symmetry-breaking transitions in equilibrium shapes of coherent precipitates: Effect of elastic anisotropy and inhomogeneity

We examine the symmetry-breaking transitions in equilibrium shapes of coherent precipitates in two-dimensional (2-D) systems under a plane-strain condition with the principal misfit strain components epsilon(xx)*. and epsilon(yy)*. For systems with cubic elastic moduli, we first show all the shape transitions associated with different values of t = epsilon(yy)*/epsilon(xx)*. We also characterize each of these transitions, by studying its dependence on elastic anisotropy and inhomogeneity. For systems with dilatational misfit (t = 1) and those with pure shear misfit (t = -1), the transition is from an equiaxed shape to an elongated shape, resulting in a break in rotational symmetry. For systems with nondilatational misfit (-1 < t < 1; t not equal 0), the transition involves a break in mirror symmetries normal to the x- and y-axes. The transition is continuous in all cases, except when 0 < t < 1. For systems which allow an invariant line (-1 less than or equal to t < 0), the critical size increases with an increase in the particle stiffness. However, for systems which do not allow an invariant line (0 < t less than or equal to 1), the critical size first decreases, reaches a minimum, and then starts increasing with increasing particle stiffness; moreover, the transition is also forbidden when the particle stiffness is greater than a critical value.

An extended Cahn-Hilliard model for interfaces with cubic anisotropy

For studying systems with a cubic anisotropy in interfacial energy sigma, we extend the Cahn-Hilliard model by including in it a fourth-rank term, namely, gamma (ijlm) [partial derivative (2) c/(partial derivativex(i) partial derivativex(j))] [partial derivative (2) c/(partial derivativex(l) partial derivativex(m))]. This term leads to an additional linear term in the evolution equation for the composition parameter field. It also leads to an orientation-dependent effective fourth-rank coefficient gamma ([hkl]) in the governing equation for the one-dimensional composition profile across a planar interface. The main effect of a non-negative gamma ([hkl]) is to increase both sigma and interfacial width w, each of which, upon suitable scaling, is related to gamma ([hkl]) through a universal scaling function. In this model, sigma is a differentiable function of interface orientation (n) over cap, and does not exhibit cusps; therefore, the equilibrium particle shapes (Wulff shapes) do not contain planar facets. However, the anisotropy in the interfacial energy can be large enough to give rise to corners in the Wulff shapes in two dimensions. In particles of finite sizes, the corners become rounded, and their shapes tend towards the Wulff shape with increasing particle size.

Effect of strain path change on the evolution of texture and microstructure during rolling of copper and nickel

The effect of strain path change during rolling has been investigated for copper and nickel using X-ray diffraction and electron back scatter diffraction as well as crystal plasticity simulations. Four different strain paths namely: (i) unidirectional rolling; (ii) reverse rolling; (iii) two-step cross rolling and (iv) multi-step cross rolling were employed to decipher the effect of strain path change on the evolution of deformation texture and microstructure. The cross rolled samples showed weaker texture with a prominent Bs {1 1 0}< 1 1 2 > and P(B(ND)) {1 1 0}< 1 1 1 > component in contrast to the unidirectional and reverse rolled samples where strong S {1 2 3}< 6 3 4 > and Cu {1 1 2}< 1 1 1 > components were formed. This was more pronounced for copper samples compared to nickel. The cross rolled samples were characterized by lower anisotropy and Taylor factor as well as less variation in Lankford parameter. Viscoplastic self-consistent simulations indicated that slip activity on higher number of octahedral slip systems can explain the weaker texture as well as reduced anisotropy in the cross rolled samples. (C) 2011 Elsevier B.V. All rights reserved.

Dynamic contact angle beating from drops impacting onto solid surfaces exhibiting anisotropic wetting

This paper reports an experimental investigation of low Weber number water drops impacting onto solid surfaces exhibiting anisotropic wetting. The wetting anisotropy is created by patterning the solid surfaces with unidirectional parallel grooves. Temporal measurements of impacting drop parameters such as drop base contact diameter, apparent contact angle of drop, and drop height at the center are obtained from high-speed video recordings of drop impacts. The study shows that the impact of low Weber number water drops on the grooved surface exhibits beating phenomenon in the temporal variations of the dynamic contact angle anisotropy and drop height at the center of the impacting drop. It is observed that the beating phenomenon of impacting drop parameters is caused by the frequency difference between the dynamic contact angle oscillations of impacting drop liquid oriented perpendicular and parallel to the direction of grooves on the grooved surface. The primary trigger for the phenomenon is the existence of non-axisymmetric drop flow on the grooved surface featuring pinned and free motions of drop liquid in the directions perpendicular and parallel to the grooves, respectively. The beat frequency is almost independent of the impact drop Weber number. Further experimental measurements with solid surfaces of different groove textures show that the grooved surface with larger wetting anisotropy may be expected to show a dominant beating phenomenon. The phenomenon is gradually damped out with time and is fully unrecognizable at higher drop impact Weber numbers. (C) 2011 Elsevier B.V. All rights reserved.

Interaction anisotropy and shear instability of aspirin polymorphs established by nanoindentation

Nanoindentation is applied to the two polymorphs of aspirin to examine and differentiate their interaction anisotropy and shear instability. Aspirin provides an excellent test system for the technique because: (i) polymorphs I and II exhibit structural similarity in two dimensions, thereby facilitating clear examination of the differences in mechanical response in relation to well-defined differences between the two crystal structures; (ii) single crystals of the metastable polymorph II have only recently become accessible; (iii) shear instability has been proposed for II. Different elastic moduli and hardness values determined for the two polymorphs are correlated with their crystal structures, and the interpretation is supported by measured thermal expansion coefficients. The stress-induced transformation of the metastable polymorph II to the stable polymorph I can be brought about rapidly by mechanical milling, and proceeds via a slip mechanism. This work establishes that nanoindentation provides ``signature'' responses for the two aspirin polymorphs, despite their very similar crystal structures. It also demonstrates the value of the technique to quantify stability relationships and phase transformations in molecular crystals, enabling a deeper understanding of polymorphism in the context of crystal engineering.

Magnetic and Mechanical Anisotropy in a Manganese 2-Methylsuccinate Framework Structure

Hybrid inorganic-organic framework materials exhibit unique properties that can be advantageously tuned through choice of the inorganic and organic components and by control of the crystal structure. We present a new hydrothermally prepared 3D hybrid framework, [Mn(2-methylsuccinate)](n) (1), comprising alternating 2D manganese oxide sheets and isolated MnO(6) octahedra, pillared via syn, anti-syn carboxylates. Powder magnetic characterization shows that the compound is a homospin Mn(II) ferrimagnet below 2.4 K. The easy-axis is revealed by single-crystal magnetic susceptibility studies and a magnetic structure is proposed. Anisotropic elastic moduli and hardness, observed through nanoindentation on differing crystal facets, were correlated with specific structural features. Such measurements of anisotropy are not commonly undertaken, yet allow for a more comprehensive understanding of structure-property relationships.