2020, Meylan, C.M., Orava, J., Greer, A.L.

We explore the glassy states achievable after a metallic glass is formed on liquid quenching. Samples of La55Al25Ni20 (at.%) metallic glass (rod and ribbon) are studied. The extent of structural relaxation at room temperature is characterized for this low-glass-transition temperature glass. Plastic deformation (uniaxial compression) rejuvenates the glass to states of higher enthalpy characteristic of glass formation at high cooling rate. Deformation increases the heterogeneity of the glass, widening the spectrum of relaxation times. The extent of rejuvenation in samples of low aspect ratio is compared with that under conditions of high constraint in notched samples. The deformation-induced rejuvenation is particularly susceptible to reduction on subsequent ageing. Fast-scanning calorimetry is useful in characterizing the dynamics of structural relaxation. The shadow glass transition is more evident on fast heating, and is observed in this glass for the first time. A new excess exothermic effect is observed before the glass transition.

2022, Costa, Miguel B., Londoño, Juan J., Blatter, Andreas, Hariharan, Avinash, Gebert, Annett, Carpenter, Michael A., Greer, A. Lindsay

Cryogenic thermal cycling (CTC) is an effective treatment for improving the room-temperature plasticity and toughness in metallic glasses. Despite considerable attention to characterizing the effects of CTC, they remain poorly understood. A prominent example is that, contrary to expectation, the stored energy in a metallic glass first rises, and then decreases, as CTC progresses. In this work, CTC is applied to bulk metallic glasses based on Pd, Pt, Ti, or Zr. The effects on calorimetric and mechanical properties are evaluated. Critically, CTC-induced effects, at whatever stage, are found to decay over about one week at room temperature after CTC, returning the properties to those of the as-cast glass. A model is proposed for CTC-induced effects, treating them as analogous to the accumulation of anelastic strain. The implications for analysis of existing data, and for future research on CTC effects, are highlighted.

2020, Robertson, Christopher G., Vaikuntam, Sankar Raman, Heinrich, Gert

We describe an approach for modeling the filler network formation kinetics of particle-reinforced rubbery polymers—commonly called filler flocculation—that was developed by employing parallels between deformation effects in jammed particle systems and the influence of temperature on glass-forming materials. Experimental dynamic viscosity results were obtained concerning the strain-induced particle network breakdown and subsequent time-dependent reformation behavior for uncross-linked elastomers reinforced with carbon black and silica nanoparticles. Using a relaxation time function that depends on both actual dynamic strain amplitude and fictive (structural) strain, the model effectively represented the experimental data for three different levels of dynamic strain down-jump with a single set of parameters. This fictive strain model for filler networking is analogous to the established Tool–Narayanaswamy–Moynihan model for structural relaxation (physical aging) of nonequilibrium glasses. Compared to carbon black, precipitated silica particles without silane surface modification exhibited a greater overall extent of filler networking and showed more self-limiting behavior in terms of network formation kinetics in filled ethylene-propylene-diene rubber (EPDM). The EPDM compounds with silica or carbon black filler were stable during the dynamic shearing and recovery experiments at 160 °C, whereas irreversible dynamic modulus increases were noted when the polymer matrix was styrene-butadiene rubber (SBR), presumably due to branching/cross-linking of SBR in the rheometer. Care must be taken when measuring and interpreting the time-dependent filler networking in unsaturated elastomers at high temperatures.