Shear-induced Phase Transition Research Articles

Shear-induced phase transition in the aqueous solution of an imidazolium-based ionic liquid.

An ionic liquid (IL) is a salt in the liquid state that consists of a cation and an anion, one of which possesses an organic component. Because of their non-volatile property, these solvents have a high recovery rate, and, hence, they are considered as environment-friendly green solvents. It is necessary to study the detailed physicochemical properties of these liquids for designing and processing techniques and find suitable operating conditions for IL-based systems. In the present work, the flow behavior of aqueous solutions of an imidazolium-based IL, 1-methyl-3-octylimidazolium chloride, is investigated, where the dynamic viscosity measurements indicate non-Newtonian shear thickening behavior in the solutions. Polarizing optical microscopy shows that the pristine samples are isotropic and transform into anisotropic after shear. These shear thickened liquid crystalline samples change into an isotropic phase upon heating, which is quantified by the differential scanning calorimetry. The small angle x-ray scattering study revealed that the pristine isotropic cubic phase of spherical micelles distort into non-spherical micelles. This has provided the detailed structural evolution of mesoscopic aggregates of the IL in an aqueous solution and the corresponding viscoelastic property of the solution.

Shear-induced phase transition and critical exponents in three-dimensional fiber networks.

When subject to applied strain, fiber networks exhibit nonlinear elastic stiffening. Recent theory and experiments have shown that this phenomenon is controlled by an underlying mechanical phase transition that is critical in nature. Growing simulation evidence points to non-mean-field behavior for this transition and a hyperscaling relation has been proposed to relate the corresponding critical exponents. Here, we report simulations on two distinct network structures in three dimensions. By performing a finite-size scaling analysis, we test hyperscaling and identify various critical exponents. From the apparent validity of hyperscaling, as well as the non-mean-field exponents we observe, our results suggest that the upper critical dimension for the strain-controlled phase transition is above three, in contrast to the jamming transition that represents another athermal, mechanical phase transition.

Thermodynamics of shear-induced phase transition of polydisperse soft particle glasses

The thermodynamics of the shear-induced phase transition of soft particle glasses is presented. Jammed suspensions of soft particles transform into a layered phase in a strong shear flow from a stable glassy phase at lower shear rates. The thermodynamics of the two phases can be computed based on the elastic energy and excess entropy of the system. At a critical shear rate, the elastic energy, the excess entropy, the free energy, the temperature, and the shear stress undergo discontinuous jumps at the phase transitions from the glassy to the layered phase. An effective temperature is defined from the derivative of the elastic energy and the excess entropy. The Helmholtz free energy is constructed using the elastic energy, excess entropy, and derived temperature. At a fixed shear rate, there is no equilibrium between the states. However, at a fixed temperature, the glassy and layered states may coexist, as indicated by the equality of their Helmholtz free energies. While this first-order phase transition is possible, it cannot be observed in simple shear because the stress is the same in both phases at the same temperature. Thus, shear banding cannot be observed in this system. Finally, an equation of state, which relates the shear stress to the excess entropy, is presented. This equation of state shows that all dynamical properties (e.g., shear-induced diffusivity and first and second normal stresses) of these jammed non-Brownian suspensions can be determined solely by measuring the shear stress.

Multi-Color Photoluminescence Based on Mechanically and Thermally Induced Liquid-Crystalline Phase Transitions of a Hydrogen-Bonded Benzodithiophene Derivative.

Controlling assembled structures of π-conjugated liquid-crystalline molecules is of great interest in the development of stimuli-responsive luminescent materials due to their molecular motility in the ordered states. Herein, we describe a mechanoresponsive hydrogen-bonded benzodithiophene liquid-crystalline molecule that exhibits a tricolor photoluminescence switching at ambient temperature. The compound shows a shear-induced phase transition from a rectangular columnar to a metastable optically anisotropic mesophase, which is accompanied by the luminescent color change from yellow to sky-blue. The metastable mesophase exhibits a time-responsive transformation to another metastable mesophase showing a blue-green emission through isothermal aging at room temperature. The luminescent color of aged sample reverts back to the initial yellow color by thermal annealing at 150 °C. These dynamic structural changes accompanied by the emission color changes are governed by distinct π-stacking modes and hydrogen-bonded patterns. The shear-induced luminescent color change from yellow to blue is found to occur above the shear strain of 390 % at which the shear stress is 2.4×105 Pa as determined from dynamic viscoelastic measurements.

Shear-induced liquid-crystalline phase transition behaviour of colloidal solutions of hydroxyapatite nanorod composites.

Liquid-crystalline (LC) bio-inspired materials based on colloidal nanoparticles with anisotropic morphologies such as sheets, plates, rods and fibers were used as functional materials. They show stimuli-responsive behaviour under mechanical force and in electric and magnetic fields. Understanding the effects of external stimuli on the structures of anisotropic colloidal particles is important for the development of highly ordered structures. Recently, we have developed stimuli-responsive hydroxyapatite (HAP)-based colloidal LC nanorods that are environmentally-friendly functional materials. In the present study, the ordering behaviour of HAP nanorod dispersions, which show LC states, has been examined using in situ small-angle neutron scattering and rheological measurements (Rheo-SANS) under shearing force. The structural analyses and dynamic viscosity observations provided detailed information about the effects of shear force on the structural changes of HAP nanorods in D2O dispersion. The present Rheo-SANS measurements unraveled three kinds of main effects of the shear force: the enhancement of interactions between the HAP nanorods, the alignment of HAP nanorods to the shear flow direction, and the formation and disruption of HAP nanorod assemblies. Simultaneous analyses of dynamic viscosity and structural changes revealed that the HAP nanorod dispersions exhibited distinctive rheological properties accompanied by their ordered structural changes.

Shear-induced martensitic transformations in crystalline polyethylene: Direct molecular-dynamics simulations

For the first time, we carry out molecular dynamics (MD) simulation of shear-induced martensitic phase transitions between the orthorhombic and non-orthorhombic (triclinic and monoclinic) phases of crystalline polyethylene (PE) in the framework of a realistic all atom model of the polymer. We show that the variation of the shear rate allows observing on a nano-sample both a strongly nonequilibrium phase transition occurring by random nucleation and irregular growth of a new phase ('civilian' way, for rapid deformations) and the coherent, or 'military', kinetics (generally considered as usual for martensitic transformations). We induce transitions from the orthorhombic to the triclinic phase according to two transformation modes observed in experiment on PE single crystals. Rapid deformation favors the transition directly to the triclinic phase, slow deformation - first to the intermediate monoclinic, and only then - to the triclinic phase. The second way corresponds to the experiment on extended chain PE. We explain this result and analyze the competition between different transformation and plastic deformation modes. Rotations of PE chains around their axes necessary for the transition between the orthorhombic and non-orthorhombic phases are executed by short twist defects diffusing along the chains. The transition between the monoclinic and triclinic phases occurs through half-chain-period translations of the chains along their axes, mostly collectively, as crystallographic slips.

Shear-Induced First-Order Transition in Polar Liquid Crystals.

The hydrodynamic theory of polar liquid crystals is widely used to describe biological active fluids as well as passive molecular materials. Depending on the "shear-alignment parameter", in passive or weakly active polar fluids under external shear, the polar order parameter p is either inclined to the flow at a fixed (Leslie) angle, or rotates continuously. Here, we study the role of an additional "shear-elongation parameter" that has been neglected in the recent literature and causes |p| to change under flow. We show that this effect can give rise to a shear-induced first-order phase transition from isotropic to polar, and significantly change the rheological properties of both active and passive polar fluids.

Shear-induced structural and thermodynamic phase transitions in micellar systems.

In this contribution a methodology to compute and classify shear-induced structural and phase transitions in surfactant/water mixtures from rheological measurements is presented. Non-linear rheological experiments, considering variations in surfactant concentration and temperature, are analyzed. In particular, the parameters of the BMP (Bautista-Manero-Puig) model, obtained from the fitting of the shear stress versus shear rate data, which are functions of surfactant concentration and temperature, allow classifying structural and phase transition boundaries. To test this methodology, we consider the analysis of the shear-induced structural and phase transitions of two micellar systems, cetyltrimethylammonium tosylate (CTAT)/water as a function of CTAT concentrations and Pluronics P103/water as a function of temperature. We found that the CTAT/water system presents a first-order phase transition at 30 ° C, and around 31 to 32 wt.% from isotropic to nematic phases, whereas a 20 wt.% Pluronics P103 aqueous micellar solution has two second-order (structural) phase transitions, one from spherical to cylindrical micelles at 33.1 ° C, and another one from cylindrical micelles to a nematic phase at 35.8 ° C and one first-order phase transition around 37.9 ° C at high shear rates near to the cloud point previously reported. The proposed methodology is also able to identify the instability regions where the wormlike micelles are broken, producing the typical shear banding behavior.

A theoretical prediction on the shear-induced phase transformation of TKX-50.

Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) is a new and attractive energetic material that outperforms numerous common explosives because of its excellent properties and performance, and is thus a promising candidate to replace some of them. Nevertheless, knowledge of its physico-chemical properties, in particular, the underlying mechanism for it undergoing external stimuli for complete decay still remains poor. In the present study, we ascertain a preferred slip system of (010)/[101] and a shear-induced phase transition of TKX-50 with the aid of theoretical calculations. In other words, a new phase of TKX-50, γ-TKX-50, is observed to be formed by shearing TKX-50 along a slip system of (010)/[101] or (010)/[101[combining macron]] with a space group of P21/a, elevated energy of 9.4 kcal mol-1 and a unit cell expanded 4%, relative to the original TKX-50. Moreover, γ-TKX-50 can most readily be formed by shearing TKX-50 along (010)/[101] with a lowest energy barrier of 18.6 kcal mol-1, which is much below that for TKX-50 decay. The predicted elastic constants of γ-TKX-50 verify its mechanical stability with decreased mechanical anisotropy relative to the original TKX-50. In addition, we find that, after phase transition, the hydrogen bonding is weakened, while the electrostatic repulsion of Hδ+Hδ+ increases, which disfavors the proton transfer from NH3OH+ to C2O2N82- to facilitate the thermal decay of TKX-50. This suggests that the shear-induced transition from TKX-50 to γ-TKX-50 can enhance thermal stability by elevating the energy barrier for proton transfer, potentially contributing to the low mechanical sensitivity of TKX-50. Hopefully, this study would enrich the insight into the underlying mechanism of TKX-50 against external thermal-mechanical stimuli. Moreover, in combination with the newly found heat-induced phase, the shear-induced phase observed in the present study and the original one, there are at least three phases for TKX-50.

Shear-Induced Isostructural Phase Transition and Metallization of Layered Tungsten Disulfide under Nonhydrostatic Compression

Pressure-induced structural and electronic transformations of tungsten disulfide (WS2) have been studied to 60 GPa, in both hydrostatic and nonhydrostatic conditions, using four-probe electrical resistance measurements, micro-Raman spectroscopy, and synchrotron X-ray diffraction. The results show the evidence for an isostructural phase transition from hexagonal 2Hc phase to hexagonal 2Ha phase, which accompanies the metallization at ∼37 GPa. This isostructural transition occurs displacively over a large pressure range between 15 and 45 GPa and is driven by the presence of strong shear stress developed in the layer structure of WS2 under nonhydrostatic compression. Interestingly, this transition is absent in hydrostatic conditions using He pressure medium, underscoring its strong dependence on the state of stress. We attribute the absence to the incorporation of He atoms between the layers, mitigating the development of shear stress. We also conjecture a possibility of magnetic ordering in WS2 that may occ...

Columnar liquid-crystalline assemblies of X-shaped pyrene–oligothiophene conjugates: photoconductivities and mechanochromic functions

The self-assembly of X-shaped pyrene–oligothiophene conjugated molecules results in the formation of columnar liquid-crystalline structures that exhibit hole carrier transport properties and shear-induced phase transition accompanied by the luminescent colour change.

Homogeneous shear-driven reversible α-to-α″ phase transformation and superelasticity of titanium investigated by molecular dynamics simulations

Shear is one of the most fundamental deformation modes in solid-state phase transitions and greatly influences the transformation process and mechanism. We employed molecular dynamics simulations to investigate the reversible α-to-α″ phase transitions driven by homogeneous shear at different temperatures from 200 to 500K. The simulation results clarified the phase transformation mechanism and its reverse transformation mechanism as well as the associated crystallographic orientation relationships. The transformation mechanism is analogous to the reorientation of α-Ti upon shock loading either experimentally or in a simulation, manifesting the validity of our simulation results. The reverse transformation mechanism indicates two transformation paths that vary with temperature, leading to two types of stress–strain curves upon unloading. The stress–strain relationships at different temperatures reveal superior superelasticity at low temperatures (200–300K) and inferior superelasticity at high temperatures (350–500K). The temperature effect on the shear-induced phase transition and superelasticity was also elucidated. The simulation results provide new insights into the stress-induced phase transition and superelasticity of Ti.

Shear Thickening in Concentrated Soft Sphere Colloidal Suspensions: A Shear Induced Phase Transition

A model of shear thickening in dense suspensions of Brownian soft sphere colloidal particles is established. It suggests that shear thickening in soft sphere suspensions can be interpreted as a shear induced phase transition. Based on a Landau model of the coagulation transition of stabilized colloidal particles, taking the coupling between order parameter fluctuations and the local strain-field into account, the model suggests the occurrence of clusters of coagulated particles (subcritical bubbles) by applying a continuous shear perturbation. The critical shear stress of shear thickening in soft sphere suspensions is derived while reversible shear thickening and irreversible shear thickening have the same origin. The comparison of the theory with an experimental investigation of electrically stabilized colloidal suspensions confirms the presented approach.

Identifying the role of terahertz vibrations in metal-organic frameworks: from gate-opening phenomenon to shear-driven structural destabilization.

We present an unambiguous identification of low-frequency terahertz vibrations in the archetypal imidazole-based metal-organic framework (MOF) materials: ZIF-4, ZIF-7, and ZIF-8, all of which adopt a zeolite-like nanoporous structure. Using inelastic neutron scattering and synchrotron radiation far-infrared absorption spectroscopy, in conjunction with density functional theory (DFT), we have pinpointed all major sources of vibrational modes. Abinitio DFT calculations revealed the complex nature of the collective THz modes, which enable us to establish detailed correlations with experiments. We discover that low-energy conformational dynamics offers multiple pathways to elucidate novel physical phenomena observed in MOFs. New evidence demonstrates that THz modes are intrinsically linked, not only to anomalous elasticity underpinning gate-opening and pore-breathing mechanisms, but also to shear-induced phase transitions and the onset of structural instability.

Pressure-induced phase transition and polymerization of tetracyanoethylene (TCNE)

We have studied the pressure-induced physical and chemical transformations of tetracyanoethylene (TCNE or C6N4) in diamond anvil cells using micro-Raman spectroscopy, laser-heating, emission spectroscopy, and synchrotron x-ray diffraction. The results indicate that TCNE in a quasi-hydrostatic condition undergoes a shear-induced phase transition at 10 GPa and then a chemical change to two-dimensional (2D) C=N polymers above 14 GPa. These phase and chemical transformations depend strongly on the state of stress in the sample and occur sluggishly in non-hydrostatic conditions over a large pressure range between 7 and 14 GPa. The x-ray diffraction data indicate that the phase transition occurs isostructurally within the monoclinic structure (P21∕c) without any apparent volume discontinuity and the C=N polymer is highly disordered but remains stable to 60 GPa-the maximum pressure studied. On the other hand, laser-heating of the C=N polymer above 25 GPa further converts to a theoretically predicted 3D C-N network structure, evident from an emergence of new Raman νs(C-N) at 1404 cm(-1) at 25 GPa and the visual appearance of translucent solid. The C-N product is, however, unstable upon pressure unloading below 10 GPa, resulting in a grayish powder that can be considered as nano-diamonds with high-nitrogen content at ambient pressure. The C-N product shows a strong emission line centered at 640 nm at 30 GPa, which linearly shifts toward shorter wavelength at the rate of -1.38 nm∕GPa. We conjecture that the observed red shift upon unloading pressure is due to increase of defects in the C-N product and thereby weakening of C-N bonds.

Shear-induced phase transition of nanocrystalline hexagonal boron nitride to wurtzitic structure at room temperature and lower pressure

Disordered structures of boron nitride (BN), graphite, boron carbide (BC), and boron carbon nitride (BCN) systems are considered important precursor materials for synthesis of superhard phases in these systems. However, phase transformation of such materials can be achieved only at extreme pressure-temperature conditions, which is irrelevant to industrial applications. Here, the phase transition from disordered nanocrystalline hexagonal (h)BN to superhard wurtzitic (w)BN was found at room temperature under a pressure of 6.7 GPa after applying large plastic shear in a rotational diamond anvil cell (RDAC) monitored by in situ synchrotron X-ray diffraction (XRD) measurements. However, under hydrostatic compression to 52.8 GPa, the same hBN sample did not transform to wBN but probably underwent a reversible transformation to a high-pressure disordered phase with closed-packed buckled layers. The current phase-transition pressure is the lowest among all reported direct-phase transitions from hBN to wBN at room temperature. Usually, large plastic straining leads to disordering and amorphization; here, in contrast, highly disordered hBN transformed to crystalline wBN. The mechanisms of strain-induced phase transformation and the reasons for such a low transformation pressure are discussed. Our results demonstrate a potential of low pressure-room temperature synthesis of superhard materials under plastic shear from disordered or amorphous precursors. They also open a pathway of phase transformation of nanocrystalline materials and materials with disordered and amorphous structures under extensive shear.

Twinning hierarchy, shape memory, and superelasticity demonstrated by molecular dynamics

A martensitic phase transition exhibiting shape memory, transformation-induced plasticity, or superelasticity typically involves a transformation between a high temperature, high symmetry phase and a low temperature, low symmetry phase. There have been numerous attempts using molecular dynamics to simulate the shape memory behavior, where the memory is stored in a twinned martensite and deformation occurs by motion of twin boundaries. However, the 3D case has always proved elusive, because suitable interatomic potentials to produce a unique low temperature phase are difficult to obtain. Here we present a study in which the binary Morse potential is tuned specifically to maximize the difference between L1${}_{0}$ and B19 (Strukturbericht notation, spacegroups P4/mmm and Pmma) structures. The twinned structure of martensite has been induced by gradually cooling the sample below the transition temperature. A bar-shaped sample was plastically deformed in the martensite phase, and on reheating above the transition temperature the initial shape was recovered. The effect of the shear-induced phase transition on the nanostructure of resulting martensite has also been investigated. An unusual discovery is that of a hierarchy of twins: nanotwins accommodate the mismatch between austenite and martensite at the habit plane, while dynamically created macrotwins are responsible for the deformation behavior and shape memory.

Shear-induced lamellar ordering and interfacial sliding in amorphous carbon films: A superlow friction regime

A shear-induced phase transition from disorder to lamellar ordering in amorphous carbon films are investigated by molecular dynamics simulations. Formation of well-separated graphene-like interfacial layers is observed with large interlayer distances, diminishing and ultimately vanishing interlayer bonds, which provides a near-frictionless sliding plane. The steady-state velocity accommodation mode after the running-in stage is interfacial sliding between the graphene-like layers, which explains the experimentally observed graphitization and formation of carbon-rich transfer layers. A superlow friction or superlubricity regime with friction coefficient of approximately 0.01 originates from the extremely large repulsive and low shear interactions across the sliding interface.

Microphase transitions of block copolymer/nanorod composites under shear flow

The shear-induced reorientations and phase transitions of symmetric diblock copolymer/nanorod nanocomposites subjected to steady shear flow, are systematically investigated via dissipative particle dynamics (DPD) simulation method. Both selective and nonselective nanorods (NRs) are considered, with low and high NRs concentrations. To preserve lamellar morphology in the nanocomposites, the NRs concentration is controlled below 15%. The final morphologies of nanocomposites depend on the interplay between NRs and diblock copolymers (DBCPs) under shear flow. The cooperatively induced microphase structures include lamellar (parallel, diagonal and perpendicular alignment), ribbon and cylindrical phases. The presence of anisotropic NRs not only delays or advances the shear-induced transition in lamellae orientation, but also induces the phase transitions by changing the effective composition of the copolymers (feff) in nanocomposites. Meanwhile, the low viscosity in the perpendicular lamellae of DBCPs provides an energetic reason for the lamellae changing into perpendicular orientation, with the shear thinning. The shear thinning corresponds to the reorientation of the lamellae, while the shear thickening corresponds to the phase transition from lamellar to ribbon, and to cylindrical structure.

Gradient and vorticity banding

Banded structures of macroscopic dimensions can be induced by simple shear flow in many different types of soft matter systems. Depending on whether these bands extend along the or direction, the transition is referred to as gradient banding or vorticity banding, respectively. The main features of can be understood on the basis of a relatively simple constitutive equation. This minimal model for will be discussed in some detail, and its predictions are shown to explain many of the experimentally observed features. The minimal model assumes a decrease of the shear stress of the homogeneously sheared system with increasing shear rate within a certain shear-rate interval. The possible microscopic origin of the severe shear-thinning behaviour that is necessary for the resulting nonmonotonic flow curves is discussed for a few particular systems. Deviations between experimental observations and predictions by the minimal model are due to obvious simplifications within the scope of the minimal model. The most serious simplifications are the neglect of concentration dependence of the shear stress (or on other degrees of freedom) and of the elastic contributions to the stress, normal stresses, and the possibility of shear-induced phase transitions. The consequences of coupling of stress and concentration will be analyzed in some detail. In contrast to predictions of the minimal model, when coupling to concentration is important, a flow instability can occur that does not require strong shear thinning. Gradient is sometimes also observed in glassy- and gel-like systems, as well as in shear-thickening systems. Possible mechanisms that could be at the origin of gradient-band formation in such systems are discussed. Gradient can also occur in strongly entangled polymeric systems. Banding in these systems is discussed on the basis of computer simulations. Vorticity is less well understood and less extensively investigated experimentally as compared to banding. Possible scenarios that are at the origin of will be discussed. Among other systems, the observed vorticity-banding transition in rod-like colloids is discussed in some detail. It is argued, on the basis of experimental observations for these colloidal systems, that the vorticity-banding instability for such colloidal suspensions is probably related to an elastic instability, reminiscent of the Weissenberg effect in polymeric systems. This mechanism might explain in discontinuously shear-thickening systems and could be at work in other vorticity-banding systems as well. This overview does not include time-dependent phenomena like oscillations and chaotic behaviour.