Connecting Active-Site Loop Conformations and Catalysis in Triosephosphate Isomerase: Insights from a Rare Variation at Residue96 in the Plasmodial Enzyme

Despite extensive research into triosephosphate isomerases (TIMs), there exists a gap in understanding of the remarkable conjunction between catalytic loop-6 (residues 166-176) movement and the conformational flip of Glu165 (catalytic base) upon substrate binding that primes the active site for efficient catalysis. The overwhelming occurrence of serine at position96 (98% of the 6277 unique TIM sequences), spatially proximal to E165 and the loop-6 residues, raises questions about its role in catalysis. Notably, Plasmodium falciparum TIM has an extremely rare residuephenylalanineat this position whereas, curiously, the mutant F96S was catalytically defective. We have obtained insights into the influence of residue96 on the loop-6 conformational flip and E165 positioning by combining kinetic and structural studies on the PfTIM F96 mutants F96Y, F96A, F96S/S73A, and F96S/L167V with sequence conservation analysis and comparative analysis of the available apo and holo structures of the enzyme from diverse organisms.

Indentation Creep Behavior in Ce-Based Bulk Metallic Glasses at Room Temperature

The room temperature creep behaviors of Ce-based bulk metallic glasses were examined by the use of nanoindentation. The creep rate and creep rate sensitivity of Ce-based BMGs were derived from indentation creep curves. The low creep rate sensitivity of Ce-based BMGs indicates that the room temperature creep is dominated by localized shear flow. The experimental creep curves can be described by a generalized Kelvin model. Furthermore, the creep retardation spectrum is calculated for the Ce-based metallic glasses. The results showed that creep retardation spectrum consists of two relatively separated peaks with the well defined characteristic relaxation times.

Ductile Metallic Glasses in Supercooled Martensitic Alloys

We report ductile bulk metallic glasses based on martensitic alloys. The slowly cooled specimens contain a mixture of parent 'austenite' and martensite phase. The slightly faster cooled bulk metallic glasses with 2-5 nm sized 'austenite'-like crystalline cluster reveal high strength and large ductility (16%). Shear bands propagate in a slither mode in this spatially inhomogeneous glassy structure and undergo considerable 'thickening' from 5-25 nm. A 'stress induced displacive transformation' is proposed to be responsible for both plasticity and work-hardening-like behavior of these 'M-Glasses'.

Characterization of Plastic Flow in Two Zr-Based Bulk Metallic Glasses

Plastic deformation behaviors of Zr65Al10Ni10CU15 and Zr52.5Al10Ni10Cu15Be12.5 bulk metallic glasses (BMGs) are studied by using the depth-sensing nanoindentation, microindentation and uniaxial compression. The Be-containing BMG exhibits a significantly improved overall plastic strain compared with the Be-free alloy during compressive tests. Both BMGs show a loading-rate-dependent serrated flow during nanoindentation measurements, but the Be-containing alloy exhibits a much lower critical loading rate for the disappearance of the serration than the Be-free BMG. The shear band patterns developed during plastic deformation are investigated by microindentation technique, wherein much higher shear band density is found in the Be-containing alloy than in the Be-free alloy, indicating an easier nucleation of shear bands in the former BMG. The difference in the plastic deformation behavior of the two BMGs can be explained by a free volume model.

Deformation Morphology Underneath the Vickers Indent in Bulk Metallic Glasses

Plastic deformation behaviour of Zr52.5Al10Ni10Cu15Be12.5 and Mg65Cu25Gd10 bulk metallic glasses (BMGs) is studied by using the depth-sensing nanoindentation and microindentation. The subsurface plastic deformation zone of the BMGs is investigated using the bonded interface technique. Both the BMGs exhibit the serrated flow depending on the loading rate in the loading process of indentation. Slow indentation rates promote more conspicuous serrations, and rapid indentations suppress the serrated flow. Mg-based BMG shows a much higher critical loading rate for the disappearance of the serration than that in Zr-based BMG. The significant difference in the shear band pattern in the subsurface plastic deformation zone is responsible for the different deformation behaviour between the two BMGs. Increase of the loading rate can lead to the increase of the density of shear bands. However, there is no distinct change in the character of shear bands at the loading rate of as high as 1000 nm/s.

Atomistic Origin Of Rate-Dependent Serrated Plastic Flow In Metallic Glasses

Nanoindentation simulations on a binary metallic glass were performed under various strain rates by using molecular dynamics. The rate-dependent serrated plastic flow was clearly observed, and the spatiotemporal behavior of its underlying irreversible atomic rearrangement was probed. Our findings clearly validate that the serration is a temporally inhomogeneous characteristic of such rearrangements and not directly dependent on the resultant shear-banding spatiality. The unique spatiotemporal distribution of shear banding during nanoindentation is highlighted in terms of the potential energy landscape (PEL) theory.

A Modified Free Volume Model For Characterizing Of Rate Effect In Bulk Metallic Glasses

We investigate the plastic deformation and constitutive behaviour of bulk metallic glasses (BMGs). A dimensionless Deborah number De(ID) = t(r)/t(i) is proposed to characterize the rate effect in BMGs, where t(r) is the structural relaxing characteristic time of BMGs under shear load, t(i) is the macroscopic imposed characteristic time of applied stress or the characteristic time of macroscopic deformation. The results demonstrate that the modified free volume model can characterize the strain rate effect in BMGs effectively.

Energy Dissipation In Fracture Of Bulk Metallic Glasses Via Inherent Competition Between Local Softening And Quasi-Cleavage

Compression, tension and high-velocity plate impact experiments were performed on a typical tough Zr41.2Ti13.8Cu10Ni12.5Be22.5 (Vit 1) bulk metallic glass (BMG) over a wide range of strain rates from similar to 10(-4) to 10(6) s(-1). Surprisingly, fine dimples and periodic corrugations on a nanoscale were also observed on dynamic mode I fracture surfaces of this tough Vit 1. Taking a broad overview of the fracture patterning of specimens, we proposed a criterion to assess whether the fracture of BMGs is essentially brittle or plastic. If the curvature radius of the crack tip is greater than the critical wavelength of meniscus instability [F. Spaepen, Acta Metall. 23 615 (1975); A.S. Argon and M. Salama, Mater. Sci. Eng. 23 219 (1976)], microscale vein patterns and nanoscale dimples appear on crack surfaces. However, in the opposite case, the local quasi-cleavage/separation through local atomic clusters with local softening in the background ahead of the crack tip dominates, producing nanoscale periodic corrugations. At the atomic cluster level, energy dissipation in fracture of BMGs is, therefore, determined by two competing elementary processes, viz. conventional shear transformation zones (STZs) and envisioned tension transformation zones (TTZs) ahead of the crack tip. Finally, the mechanism for the formation of nanoscale periodic corrugation is quantitatively discussed by applying the present energy dissipation mechanism.

Plastic deformation in Ce-based bulk metallic glasses during depth-sensing indentation

The deformation behavior and the effect of the loading rate on the plastic deformation features in (numbers indicate at.%) Ce60Al15Cu10Ni15, Ce65Al10Cu10Ni10Nb5, Ce68Al10Cu20Nb2, and Ce70Al10Cu20 bulk metallic glasses (BMGs) were investigated through nanoindentation. The load-displacement (P-h) curves of Ce65Al10Cu10Ni10Nb5, Ce68Al10Cu2, and Ce70Al10Cu20 BMGs exhibited a continuous plastic deformation at all studied loading rate. Whereas, the P-h curves of Ce60Al15Cu10Ni15 BMG showed a quite unique feature, i.e. homogeneous plastic deformation at low loading rates, and a distinct serrated flow at high strain rates. Moreover, a creep deformation during the load holding segment was observed for the four Ce-based BMGs at room temperature. The mechanism for the appearance of the "anomalous" plastic deformation behavior in the Ce-based BMGs was discussed. (c) 2006 Elsevier B.V. All rights reserved.

Critical serrated flow features during nanoindentation in La-based bulk metallic glasses

La57.6Al17.5(Cu,Ni)(24.9) and La64Al14(Cu,Ni)(22) bulk metallic glasses (BMGs) were prepared by copper-mould casting method. Plastic deformation behavior of the two BMGs at various loading rates was studied by nanoindentation. The results showed that the La57.6Al17.5(Cu,Ni)(24.9) BMG with a glass transition temperature of 423 K exhibited prominent serrated flow at low loading rates, whereas less pronounced serrated flow at high rates during nanoindentation. In contrast, the La64Al14(Cu,Ni)(22) BMG with a glass transition temperature of 401 K exhibited prominent serrated flow at high loading rates. The different rate dependency of serrated flow in the two La-based BMGs is related to the different glass transition temperature, and consequently the degree of viscous flow during indentation at room temperature. A smoother flow occurs in the alloy with relatively lower glass transition temperature, due to the relaxation of stress concentration.

An asymptotic solution of hydrodynamic equations at the mid-plane of a plume in the earths mantle

From the partial differential equations of hydrodynamics governing the movements in the Earth's mantle of a Newtonian fluid with a pressure- and temperature-dependent viscosity, considering the bilateral symmetry of velocity and temperature distributions at the mid-plane of the plume, an analytical solution of the governing equations near the mid-plane of the plume was found by the method of asymptotic analysis. The vertical distribution of the upward velocity, viscosity and temperature at the mid-plane, and the temperature excess at the centre of the plume above the ambient mantle temperature were then calculated for two sets of Newtonian rheological parameters. The results obtained show that the temperature at the mid-plane and the temperature excess are nearly independent of the rheological parameters. The upward velocity at the mid-plane, however, is strongly dependent on the rheological parameters.

The thermal and mechanical structure of a two-dimensional plume in the earths mantle

On the condition that the distribution of velocity and temperature at the mid-plane of a mantle plume has been obtained (pages 213–218, this issue), the problem of determining the lateral structure of the plume at a given depth is reduced to solving an eigenvalue problem of a set of ordinary differential equations with five unknown functions, with an eigenvalue being related to the thermal thickness of the plume at this depth. The lateral profiles of upward velocity, temperature and viscosity in the plume and the thickness of the plume at various depths are calculated for two sets of Newtonian rheological parameters. The calculations show that the precondition for the existence of the plume, δT/L 1 (L = the height of the plume, δT = lateral distance from the mid-plane), can be satisfied, except for the starting region of the plume or near the base of the lithosphere. At the lateral distance, δT, the upward velocity decreases to 0.1 – 50% of its maximum value at different depths. It is believed that this model may provide an approach for a quantitative description of the detailed structure of a mantle plume.

Serrated Plastic Flow During Nanoindentation in Nd-Based Bulk Metallic Glasses

The microstructure of Nd_{60}Al_{10}Ni_{10}Cu_{20-x}Fex (x = 0, 5, 7, 10, 15, 20) alloys can change from homogeneous phase to a composite structure consisting of amorphous phase plus clusters or nanocrystals by adjusting the Fe content. The effect of microstructure on the plastic deformation behavior in this alloy system is studied by using nanoindentation. The alloys with homogeneous amorphous structure exhibit pronounced flow serrations during the loading process of nanoindentation. The addition of Fe changes the plastic deformation behavior remarkablely. No flow serration is observed in the alloys with high Fe content for the indentation depth of 500 nm. The mechanism for the change of plastic serrated flow behavior is discussed.

CHARACTERIZATION OF SHEAR BANDS IN TWO BULK METALLIC GLASSES WITH DIFFERENT INHERENT PLASTICITY

Shear banding characterization of Zr64.13Cu15.75Ni10.12Al10 and Zr65Cu15Ni10Al10 bulk metallic glasses (BMGs) with significant difference in inherent plasticity and quite similar chemical composition was studied by depth sensitive macroindentaion tests with conical indenter. Well-developed shear band pattern can be found for both BMGs after indentation. Distinct difference in the shear band spacing, scale of plastic deformation region and the shear band branching in the two BMGs account for the different plasticity.