An official website of the United States government
We present the results of high-temperature (900°C), high-pressure (200 MPa) deformation experiments that identify the processes and deformation conditions leading to melt migration in crystal-rich mushes. This study is relevant to transport of magmas in transcrustal magma reservoirs. Experimental samples comprise juxtaposed pieces of soda-lime glass and densified mixtures of borosilicate glass and quartz sand, which, at elevated temperatures and pressures, have melt and shear viscosities similar to natural silicate melts and crystal-rich mushes. The synthetic mushes have crystal fractions of 0.60 to 0.83. Samples were deformed in torsion at shear strain rates of 10-5 to 10-4 s-1 to shear strains up to 2.7. Image analysis of experimental samples shows melt migrates into the mush during shear. In mushes with crystal fractions ≥ 0.75 shearing causes melt-filled mm-scale dikes to form and propagate into the mush. To our knowledge, these features are the first dikes formed in high-temperature, high-pressure deformation experiments. Dike formation results from shear-induced dilation, which causes the mush to become underpressurized relative to the melt, at an estimated pressure differential of 10 MPa. Experimental conditions indicate shear-induced dilation and diking occur while the mush is still viscous (i.e., Weissenberg number < 10-2). We apply our results to Soufrière Hills Volcano (Montserrat, West Indies) and use our analysis to predict the deformation conditions that would lead to diking and rapid, voluminous melt migration in that active volcanic system.
more »
« less
Shear-induced crystallization of polyamide 11
Abstract Shear-induced formation of crystal nuclei in polyamide 11 (PA 11) was studied using a conventional parallel-plate rheometer. Crystallization of PA 11 after shearing the melt at different rates for 60 s was followed by the evolution of the complex viscosity. The sheared samples showed in an optical microscope a gradient structure along the radius, due to the increasing shear rate from the center to the edge. The critical shear rate for shear-induced formation of nuclei was identified at the position where a distinct change of the semicrystalline superstructure is observed, being at around 1 to 2 s −1 . Below this threshold, a space-filled spherulitic superstructure developed as in quiescent-melt crystallization. Above this value, after shearing at rates between 1 and 5 s −1 , an increased number of point-like nuclei was detected, connected with formation of randomly oriented crystals. Shearing the melt at even higher rates led to a further increase of the nuclei number and growth of crystals oriented such that the chain axis is in parallel to the direction of flow. In addition, optical microscopy confirmed formation of long fibrillar structures after shearing at such condition. The critical specific work of flow of PA 11 was calculated to allow a comparison with that of polyamide 66 (PA 66). This comparison showed that in the case of PA 11 more work for shear-induced formation of nuclei is needed than in the case of PA 66, discussed in terms of the chemical structure of the repeat unit in the chains. Graphical abstract
more »
« less
- Award ID(s):
- 1653629
- PAR ID:
- 10320352
- Date Published:
- Journal Name:
- Rheologica Acta
- Volume:
- 60
- Issue:
- 5
- ISSN:
- 0035-4511
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Intervals of shear flow stretch polymer chains and form flow-induced precursors, which accelerate crystallization and transform the crystalline morphology from isotropic spherulites to anisotropic structures. The flow-induced crystallization of two commercial samples of isotactic polypropylene with nearly identical molecular weight distributions, differing in concentrations of catalyst residue particles, was investigated using dynamic rheology and ex situ Synchrotron X-ray scattering. Upon the application of flow, the sample with higher particle concentration crystallized at faster rates relative to the sample with lower levels of heterogenous impurities. The nucleation ability of these particles was particularly pronounced at lower levels of deformation, while flow effects became prominent as larger deformations were applied. For sufficiently strong flows ((γ ) ̇≤145 s-1), a lower critical shear stress (~0.096 MPa) was observed for the formation of shish-kebab structures in the sample with higher concentrations of particles. In this work, we have also identified the formation of shish-kebab structures in the presence of weak flow ((γ ) ̇ ≤ 0.3 s-1) when sheared for long durations of time. For equivalent levels of specific work within both flow regimes, the morphologies of these anisotropic structures were found to be characteristically distinct from one another. The long period and degree of crystallinity were also found to increase with shear stress above the stress level needed for the formation of shish-kebab structures.more » « less
-
Archaean orbicular granitoids from western Australia were investigated to better understand crystal growth processes. The orbicules are dioritic to tonalitic spheroids dispersed in a granitic host magma. Most orbicules have at least two to three concentric bands composed of elongate and radially oriented hornblendes with interstitial plagioclase. Each band consists of a hornblende-rich outer layer and a plagioclase-rich inner layer. Doublet band thicknesses increase, crystal number density decreases, and grain size increases from rim to core, suggesting crystallization was more rapid on the rims than in the core. Despite these radial differences, mineral mode and bulk composition of each band are similar, indicating limited crystal-melt segregation during crystallization. These observations lead us to suggest that the orbicules represent slowly quenched blobs of hot dioritic to tonalitic liquids injected into a cooler granitic magma. The oscillatory bands in the orbicules can be explained by rapid, disequilibrium crystallization (supercooling). In particular, a linear correlation between bandwidth and radial distance from orbicule rim can be explained by transport-limited crystallization, wherein crystallization timescales are shorter than chemical diffusion timescales. The slope of this linear relationship corresponds to the square root of the ratio between effective chemical diffusivity in the growth medium and thermal diffusivity, resulting in effective chemical diffusivities of 3 × 10−8 m2/s. These high effective diffusivities require static diffusion through a free volatile phase (fluid) and/or a strong advective/convective component in the fluid. Regardless of the mechanisms, these effective diffusivities can be used to estimate growth rates of ~10−6 m/s or 0.4 cm/hr. Our results indicate that crystals can grow rapidly, possibly facilitated by fluids and dynamic conditions. These rapid growth rates suggest that centimetre or larger crystals, such as in porphyritic and pegmatitic systems, can conceivably grow within days.more » « less
-
Pegmatites are shallow, coarse-grained magmatic intrusions with crystals occasionally approaching meters in length. Compared to their plutonic hosts, pegmatites are thought to have cooled rapidly, suggesting that these large crystals must have grown fast. Growth rates and conditions, however, remain poorly constrained. Here we investigate quartz crystals and their trace element compositions from miarolitic cavities in the Stewart pegmatite in southern California, USA, to quantify crystal growth rates. Trace element concentrations deviate considerably from equilibrium and are best explained by kinetic effects associated with rapid crystal growth. Kinetic crystal growth theory is used to show that crystals accelerated from an initial growth rate of 10−6–10−7 m s−1 to 10−5–10−4 m s−1 (10-100 mm day−1 to 1–10 m day−1), indicating meter sized crystals could have formed within days, if these rates are sustained throughout pegmatite formation. The rapid growth rates require that quartz crystals grew from thin (micron scale) chemical boundary layers at the fluid-crystal interfaces. A strong advective component is required to sustain such thin boundary layers. Turbulent conditions (high Reynolds number) in these miarolitic cavities are shown to exist during crystallization, suggesting that volatile exsolution, crystallization, and cavity generation occur together.more » « less
-
The nanoscale structure and macroscopic morphology of π-conjugated polymers are very important for their electronic application. While ordered single crystals of small molecules have been obtained via solution deposition, macroscopically aligned films of π-conjugated polymers deposited directly from solution have always required surface modification or complex pre-deposition processing of the solution. Here, ordered nanowires were obtained via shear-enhanced crystallization of π-conjugated polymers at the air–liquid–solid interface using simple deposition of the polymer solution onto an inclined substrate. The formation of macroscopically aligned nanowire arrays was found to be due to the synergy between intrinsic (π-conjugated backbone) and external (crystallization conditions) effects. The oriented nanowires showed remarkable improvement in the charge carrier mobility compared to spin-coated films as characterized in organic field-effect transistors (OFETs). Considering the simplicity and large-scale applicability, shear-enhanced crystallization of π-conjugated polymers provides a promising strategy to achieve high-performance polymer semiconductor films for electronics applications.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1007/s00397-021-01264-6
