Chemical etching of deformation sub-structures in quartz

Chemical etching of dislocations has been studied in natural and synthetic quartz single crystals, in deformed synthetic quartz and in naturally and experimentally deformed quartzites. The ability of different etchants to produce polished or preferentially etched surfaces on quartz is described. Dislocation etching was achieved on all crystal planes examined by using a saturated solution of ammonium bifluoride as the etchant. Appropriate etching times were determined for etching quartzites for grain size, subgrain boundaries, deformation lamellae, dislocations and twins. Growth and polished surfaces of synthetic single crystal quartz were similarly etched and dislocation etch pits, characteristic of various orientations were found. The use of ammonium bifluoride proved to be expecially advantageous for the basal plane, producing a polished surface with etch pits, suitable for dislocation etch pit counting. “Double” etch pits have been found on Dauphiné twin boundaries on the basal plane and the first order prism, using this etchant. Slip lines and deformation bands were suitably etched on deformed synthetic crystal surfaces for identification of the slip planes. Other acidic etchants have been explored and their application to the study of deformation structures in quartz crystals is discussed.     

The mechanisms of the formation and growth of water bubbles and associated dislocation loops in synthetic quartz

The development of water bubbles in synthetic quartz has been monitored by measurements of (i) the intensity of the light scattered and (ii) the increase in volume of the crystal, both as a function of temperature and time. These macroscopic measurements have been complemented by observations of the resulting microstructures, using transmission electron microscopy (TEM). A mechanism is proposed on the assumption that hydrogen is incorporated in the quartz structure by means of (4 H)_Si defects. On heating, these defects diffuse and clusters develop. A cluster of n(4 H)_Si produces a water bubble of (n?1)H₂O, without any change of volume of the crystal. At any temperature T there is a critical bubble diameter above which the “steam” pressure P exceeds the pressure p for a spherical bubble in mechanical equilibrium. If P becomes greater than p, then the bubble increases in volume until P=p, the increase in volume being achieved by the pipe diffusion of Si and O away from the bubble site into a linked edge dislocation loop. This process produces the observed increase in volume of the crystal. The two diffusion processes take place virtually simultaneously and continue until all the (4 H)_Si defects have been trapped in the bubbles. Values of the diffusion constant and the activation energy for the diffusion of the (4 H)_Si defects are deduced. The relevance of these observations to the hydrolytic weakening of quartz is briefly discussed.     

The solubility of [4H]Si defects in α-quartz and their role in the formation of molecular water and related weakening on heating

The nature of the solubility of water as [4H]_Si defects in quartz, and their role in providing a source of molecular water on heating, is investigated. Existing ab inito energy calculations on the incorporation of water in quartz are used to show that energetically 4H for Si substitution is likely to constitute the most prevalent mode of water uptake on the atomic scale in quartz under equilibrium conditions, and that the planar defects previously observed by a number of different authors by electron microscopy in wet quartz are likely to be planar rafts of aggregated [4H]_Si defects which are formed on supersaturation. These new conclusions call into question the previous identification of the planar defects as high pressure water clusters and require that their role in the production of molecular water in the context of recent theories of hydrolytic weakening be re-assessed. Accordingly the existing ab initio results have been used to establish the characteristics of the phase diagram for the system quartz-water in the temperature and pressure range of interest in hydrolytic weakening. Additional electron-optical experiments on wet quartz show that, on annealing at temperature in the electron microscope, similar planar defects develop in wet quartz by a diffusion process. In the context of existing theories of hydrolytic weakening it is now proposed that the conversion of [4H]_Si defects to molecular water, where this is dictated by the equilibrium phase diagram, leads to a relatively large increase in volume and to the appearance of the bubbles of free water and the nucleation of associated prismatic dislocation loops of Burgers vector b=1/3 a $\langle 11\bar 20\rangle $ as previously observed. Ultimately the development of these loops leads to dislocation-induced plasticity.     

Mechanical twinning in small quartz crystals

Quartz is known to be ferrobielastic; that is, quartz crystals have domain states (Dauphiné twins) which differ in their elastic compliance values and which can be switched by an appropriately oriented stress. Polycrystalline quartz has also been reported (Tullis 1970) to show preferential orientation of these domains following application of large uniaxial stresses. These experiments were designed to study twinning of synthetic quartz “grains” (minimum size 0.07×0.07×0.02 cm) in specially-constructed composites and of grains in three natural quartz aggregates — a quartzite, a novaculite, and a jasper. Backreflection X-ray techniques were used to verify twinning in the composite grains, while special electroding and electrical detection allowed the twinning processes to be examined in “real time.” Small synthetic quartz crystals were found to behave identically to the massive samples previously studied. Electrical pulses due to the reversal of piezoelectric coefficient d ₁₁ in twinned quartz were detected from quartzite and from the man-made composites. Novaculite also gave electrical pulses which were probably from twinning (evidenced by the correlation of expected and observed pulse sizes and shapes), while no pulses from the jaspers indicative of twinning were detected. Grain size distribution differences are considered the main structural reason for the different behaviors.     

Subgrain boundaries in quartz theoretical analysis and microscopic observations

At moderate temperature (T≈1/3 T _Melt) recovery processes become very active in wet quartz and many subgrain boundaries (sgb's) are formed which still contain interesting information on the deformation mechanisms. In particular, the geometrical characteristics of a sgb (normal, rotation axis) depend upon the glide systems which have been activated. Possible sgb's in quartz are studied from a theoretical point of view with the help of the Frank formula. The predictions are compared with observations by optical microscopy and by transmission electron microscopy (TEM) on naturally deformed quartz samples. Most of the predicted sgb's are effectively observed and there is an excellent agreement between theory and observation. This allows a rapid characterization of sgb's in tem to be performed by standard stereographic methods: only the directions of the dislocations and the plane of the sgb are determined; they are compared to a table deduced from geometrical considerations and the glide systems which have been activated during the deformation (at least the last stage of deformation) can be deduced. This method is very important for the case of quartz because the rapid irradiation of this material under the electron beam renders very difficult the characterization of the Burgers vectors of free dislocations. A similar method can be developed for observations in optical microscopy when the crystallographic orientation of the studied thin sections can be determined.     

Defects and hydrolytic weakening in α-berlinite AlPO4 a structural analog of quartz

Berlinite, AlPO₄, is a structural analog of quartz and a number of physical properties are very similar in both materials. It is thus interesting to compare their mechanical properties and investigate the possible role of water. Constant strain rate tests on wet synthetic crystals have been performed at room temperature and at 600 MPa confining pressure. They indicate that \((000){1 \mathord{\left/ {\vphantom {1 3}} \right. \kern-0em} 3}\langle 11\bar 20\rangle \) is the easy glide system. Detailled investigation of the crystal structure shows that the corresponding a dislocations can glide in such a way that only the weaker Al—O bonds are broken. This explains why this glide system is much more easily activated in berlinite than in quartz. Deformation experiments at higher temperature and at atmospheric pressure clearly show a thermally activated regime. However the actually available crystals are so rich in water that above 300° C the dislocation structure resulting from deformation is completely hidden by water precipitation and coarsening of the as-grown fluid inclusions. Like for wet quartz this later phenomenon generates numerous bubbles and sessile dislocation loops.     

Growth of quartz crystals twinned after Japan Law

The flattened or elongated morphology often observed in contact twinned crystals has been referred to the so-called re-entrant corner effect at twin junctions. To re-investigate the validity of this mechanism, natural quartz crystals twinned after Japan Law have been subjected to re-growth in a commercial synthetic quartz autoclave, and the change in their morphology and surface microtopography by re-growth studied. It is found that although twin re-entrant corners may play a role of preferential growth sites, this role can be weakened considerably and in fact can become almost negligible when crystals grow under high supersaturation condition. Preferential growth at the re-entrant corner of a twin junction is probably due to clusters of dislocations concentrated in the composition plane, and not due to the so-called re-entrant corner effect in its original sense.     

The uptake and solubility of water in quartz at elevated pressure and temperature

The uptake of water in quartz at 1.5 GPa total pressure, 1173 K and high water fugacity, over times up to 24 h, has been investigated using a newly developed assembly to prevent microcracking. It is found that the uptake is small, and below the detectability of the presently used technique of infrared spectroscopy and serial sectioning. This observation reflects either a low value for the diffusivity or the solubility or a combination of both, and is in agreement with the observations of Kronenberg et al. (1986) and Rovetta et al. (1986). It brings into question the interpretation of the early experiments on water weakening by Griggs and Blacic (1964) and the recent estimates of the solubility and diffusivity by Mackwell and Paterson (1985). Rults of a combined T.E.M., light-scattering and infrared-spectroscopy investigation of ‘wet’ synthetic quartz before and after heating at 0.1, 300 and 1500 MPa total pressure and 1173 K, strongly suggest that the water in ‘wet’ quartz is mainly in the form of H₂O in inclusions, consistent with the solubility being low, possibly less than 100 H/10⁶Si. From these observations, water-containing inclusions appear to play a major role in the plasticity of quartz, while any role of water in solid solution remains to be clarified.     

Plastic-deformati on mechanisms in quartz: The effect of water

High-temperature and pressure-deformation experiments indicate that small amounts of water strongly affect the plastic-deformation mechanisms that operate in quartz. Inherently dry natural quartz crystals exhibit a transition from T = (0001), to , t = [0001] glide at approximately 700° C at a strain rate of 8 · 10⁻⁶ sec⁻¹. The transition temperature decreases with decreasing strain rate. When water is diffused into dry natural crystals at high temperature, duplex slip occurs on the systems (0001), 112̄0and either {112̄0}, [0001] or {101̄0}, [0001] depending on which of the latter systems is most highly stressed.Hydrothermally grown synthetic quartz crystals contain relatively large amounts of structurally bound water. In these crystals, a transition occurs from (0001), 112̄0 to dominantly pencil glide in the [0001] and possibly 112̄3 directions. The transition temperature is strongly dependent on the water content of the crystals, and coincides with the hydrolytic weakening temperature defined by Griggs and Blacic for these crystals. Inhomogeneous distribution of water in the synthetic crystals controls the distribution of plastic strain and may, in part, control the orientation of subbasal deformation lamellae in these.It is suggested that anisotropic diffusion of H-OH in quartz may be responsible for the operation of the [0001] pencil-glide system in the hydrolytic weakening regime. Crystal structure anisotropy may also play a role in the slip-system transition through its influence on the Peierls stress, and this is most likely the dominant factor in the dry crystals.     

Synthetic fluid inclusions. XV. TEM investigation of plastic flow associated with reequilibration of fluid inclusions in natural quartz

The nature and abundance of dislocations in quartz surrounding fluid inclusions were studied to obtain a better understanding of processes associated with fluid inclusion reequilibration. Synthetic fluid inclusions containing 10 wt% NaCl aqueous solution were formed in three samples at 700 °C and 5 kbar. One of the samples was quenched along an isochore to serve as a reference sample. The other two samples were quenched along a P-T path that generated internal pressures in excess of the confining pressure. The two samples were held at the final reequilibration P-T conditions of 625 °C and 2 kbar for 30 and 180 days, respectively. Following the experiments, microstructures associated with fluid inclusions were examined with the TEM. Quartz in healed fractures in the reference sample that was quenched isochorically shows a moderate dislocation activity. Quartz adjacent to reequilibrated fluid inclusions in the other two samples, however, showed a marked increase in dislocation activity compared to the un-reequilibrated sample. Deformation of the inclusion walls occurred anisotropically by expansion of mobile dislocations in their slip systems. Dislocation expansion was controlled by glide in the rhombohedral planes {1 0 1 1} that was restricted to narrow zones (≤3 μm) in the immediate vicinity of the fluid inclusion walls outside of the healed fracture plane. These plastic zones were observed after both short term (30 days) and long term (180 days) experiments and are attributed to hydrolytic weakening of quartz around fluid inclusions owing to diffusion of water into the quartz matrix during the experiment. The close spatial association of submicroscopic water bubbles with dislocations, and the rarity of water bubbles in the reference sample, show clearly that in both the 30 and 180 day experiments reequilibration involves water loss from the fluid inclusions. Our results indicate that synthetic fluid inclusions in this study recover (chemically and volumetrically), even at relatively fast experimental loading rates, such that internal stresses never reach the point of brittle failure. The driving force for fluid inclusion deformation involves two related mechanisms: plastic deformation of hydrolytically weakened wet quartz in the healed fracture, and water leakage associated with preexisting and strain-induced dislocations. Received: 5 May 1998 / Accepted: 10 February 2000     

The effects of quartz recrystallization and reaction on weak phase interconnection,strain localization and evolution of microstructure

We conducted axial compression and general shear experiments, at T = 900 °C and P = 1.5 GPa, on samples of banded iron formation (BIF) and synthetic aggregates of quartz, hematite and magnetite to investigate how dynamic recrystallization of quartz promotes strain localization, and the role of weak second phases (oxides) on the rheology and microstructural evolution of the aggregates. Experiments showed strain localization into oxide rich layers, and that the oxide content and oxide distribution are key factors for the strength of the aggregate. Only 2–10 wt.% hematite leads to pronounced weakening and increasing hematite content above ∼10% has only a minor additional effect. Where oxide grains are dispersed, the initial strength contrast with quartz induces stress concentrations at their tips, promoting high stress recrystallization-accommodated dislocation creep of quartz. Fine recrystallized quartz reacts with oxide, forming trails of fine reaction product (ferrosilite/fayalite) leading to the interconnection/percolation of a weaker matrix. The strength contrast between the quartz framework and these fine-grained trails promotes strain localization into micro-shear zones, inducing drastic strain weakening. Thus dynamic recrystallization of quartz promotes syn-deformational reactions leading to a microstructurally-controlled evolution of phase strength contrast. It results in a rheologic transition from load-bearing framework to a matrix-controlled rheology, with transition from S–C′ to S–C fabric with increasing strain.     

Transmission electron microscope study of experimentally deformed K-Feldspar single crystals

Single crystals of sanidine which were experimentally deformed so as to introduce the (010)[100] slip system were examined by transmission electron microscopy (tem). Dislocation glide is mainly manifested in the samples deformed at 700° C, with a strain rate \(\dot \varepsilon = 1 - 2 \times 10^{ - 6} s^{ - 1} \) . In addition to the expected slip system another more important one, (12 \(\bar 1\) )[101], was found. The dislocations lying in (010) present a glissile dissociation. These observations have been discussed in term of the feldspar structure. Models for glissile dissociation in (010) are proposed: [100]=1/2[100]+1/2[100] or 1/2[101]+1/2[10 \(\bar 1\) ] and [101]=1/2[101]+1/2[101].     

Submicron-sized fluid inclusions and distribution of hydrous components in jadeite,quartz and symplectite-forming minerals from UHP jadeite–quartzite in the Dabie Mountains,China: TEM and FTIR investigation

Fluid inclusions and clusters of water molecules at nanometer-to submicron-scale in size have been investigated using transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) in jadeite, quartz and symplectite aegirine–augite, albite, taramite and magnetite corona minerals from ultrahigh-pressure (UHP) jadeite–quartzite at Shuanghe, the Dabie Mountains, China. Fluid inclusions from 0.003 μm to 0.78 μm in size occur in jadeite and quartz crystals, and a small number of fluid inclusions from 0.001 μm to 0.25 μm have also been detected in symplectite-forming minerals. Most of the fluid inclusions have round or negative crystal morphology and contain aqueous fluids, but some contain CO₂-rich fluids. They are usually connected to dislocations undetectable at an optical scale. The dislocations represent favorable paths for fluid leakage, accounting for non-decrepitation of most fluid inclusions when external pressure decreased at later stages, although there was partial decrepitation of some fluid inclusions unconnected to defect microstructures resulting from internal overpressure. Non-decrepitation and partial decrepitation of fluid inclusions resulted in changes of original composition and/or density. It is clear that identification of hidden re-equilibration features has significant implications for the petrological interpretation of post-peak metamorphic processes. Micro-FTIR results show that all jadeite and quartz samples contain structural water occurring as hydroxyl ions (OH⁻) and free water (H₂O) in the form of clusters of water molecules. The H₂O transformed from OH⁻ during exhumation and could have triggered and enhanced early retrograde metamorphism of the host rocks and facilitated plastic deformation of jadeite and quartz grains by dislocation movement, and thus the H₂O released during decompression might represent early-stage retrograde metamorphic fluid. The nominally anhydrous mineral (NAM) jadeite is able to transport aqueous fluids in concentrations of at least several hundred ppm water along a subduction zone to mantle depths in the form of clusters of water molecules and hydroxyl ions within crystals.     

Thermoluminescence and hydroxyl defects associated with broad-band infra red absorption in synthetic quartz

A study has been made of thermoluminescence from synthetic quartz with varying hydroxyl impurity concentrations up to approximately 300 H/10⁶ Si which are associated with a “broad-band” IR absorption in the range 2600–3700 cm⁻¹. These hydroxyl defects are known to be important in the hydrolytic weakening of quartz. We have found only minor differences in the glow curves of unheated crystals but significant intensity increases when “wet” crystals are heated sufficiently to cause bubble formation. It would seem that the electron traps are unaffected by the bubble formation, but the electron/luminescence centre radiative recombination probability is increased.     

Microstructure and fabric development in ice: Lessons learned from in situ experiments and implications for understanding rock evolution

In this contribution we present a review of the evolution of microstructures and fabric in ice. Based on the review we show the potential use of ice as an analogue for rocks by considering selected examples that can be related to quartz-rich rocks. Advances in our understanding of the plasticity of ice have come from experimental investigations that clearly show that plastic deformation of polycrystalline ice is initially produced by basal slip. Interaction of dislocations play an essential role for dynamic recrystallization processes involving grain nucleation and grain-boundary migration during the steady-state flow of ice. To support this review we describe deformation in polycrystalline ‘standard’ water-ice and natural-ice samples, summarize other experiments involving bulk samples and use in situ plane-strain deformation experiments to illustrate the link between microstructure and fabric evolution, rheological response and dominant processes. Most terrestrial ice masses deform at low shear stresses by grain-size-insensitive creep with a stress exponent (n ≤ 3). However, from experimental observations it is shown that the distribution of plastic activity producing the microstructure and fabric is initially dominated by grain-boundary migration during hardening (primary creep), followed by dynamic recrystallization during transient creep (secondary creep) involving new grain nucleation, with further cycles of grain growth and nucleation resulting in near steady-state creep (tertiary creep). The microstructural transitions and inferred mechanism changes are a function of local and bulk variations in strain energy (i.e. dislocation densities) with surface grain-boundary energy being secondary, except in the case of static annealing. As there is a clear correspondence between the rheology of ice and the high-temperature deformation dislocation creep regime of polycrystalline quartz, we suggest that lessons learnt from ice deformation can be used to interpret polycrystalline quartz deformation. Different to quartz, ice allows experimental investigations at close to natural strain rate, and through in-situ experiments offers the opportunity to study the dynamic link between microstructural development, rheology and the identification of the dominant processes.     

Dislocation structure of the deformation lamellae in synthetic quartz; a study by electron and optical microscopy

Single crystals of experimentally deformed synthetic quartz showing optical deformation lamellae were examined by transmission electron microscopy. Dislocations are distributed fairly uniformly throughout the crystal. However, parallel to the trace of the deformation lamellae, which may be irrational, there are walls of tangled dislocations whose characteristics suggest that they are directly associated with the lamellae. The nature and formation of the optical image is discussed in detail.     

A mechanism for preferential H2O leakage from fluid inclusions in quartz,based on TEM observations

Preferential leakage of H₂O from fluid inclusions containing multiple gas components has been suspected in natural metamorphic rocks and has been demonstrated experimentally for synthetic H₂O-CO₂-rich inclusions in natural quartz. Knowledge of the physical and chemical characteristics of the leakage mechanism, which may be very complex, increases the value of natural fluid inclusions to metamorphic geology. It is proposed that crystal defects play a major role in nondecrepitative preferential H₂O leakage through quartz, and remain effective during metamorphism. Inclusions with either an internal overpressure or underpressure produce strain in the adjacent quartz crystal via the nucleation of many dislocations and planar defects (like Dauphiné twin boundaries). These defects allow preferential loss of H₂O from H₂O-CO₂-rich inclusions at supercritical conditions. The transport capacity of this leakage mechanism is enhanced by nucleation of small bubbles on defect structures. The nucleation of these bubbles seems to be a recovery process in strained crystals. Solubility gradients of quartz in water in a crystal with internally underpressurized inclusions may result in optical visible implosion halos in a three dimensional spatial arrangement, caused by the growth of small bubbles at the expense of the larger original fluid inclusion. Natural fluid inclusions from Naxos (Greece) are always associated with numerous interlinked dislocations. These dislocations may have been produced by plastic derormation or by crystal growth related processes (e.g. crack healing). The presence of small bubbles on these dislocations indicates that a similar leakage mechanism for H₂O must have occurred in these rocks.     

Deformation partitioning during folding and transposition of quartz layers

Banded iron formation (BIF) from the Quadrilátero Ferrı́fero (southeastern Brazil) shows a compositional layering with alternating iron-rich and quartz-rich layers. This layering was intensively folded and transposed at a centimeter/millimeter scale through a component of bedding-parallel shear related to flexural slip at middle to high greenschist facies conditions (400–450 °C). The microstructure and c-axis fabrics of normal limbs, inverted limb and hinge zones of a selected isoclinal fold were analyzed combining optical and scanning electron microscopy (SEM) and digital image analysis. In the normal limbs, recrystallized quartz grains show undulose extinction, relatively dry grain boundaries, c-axes at high angle to foliation and a pervasive grain shape fabric (GSF) indicating operation of crystal-plastic processes. In the inverted limb, quartz grains show more serrated and porous (“wet”) grain boundaries; the GSF is similar to that of the normal limb, but c-axes are oriented at 90° to those of the normal limb. We interpreted these characteristics as reflecting operation of solution-precipitation deformation in inverted limbs, as a consequence of grains having been rotated to an orientation that was hard to basal 〈a〉 glide, but easy to dissolution-precipitation creep. This deformation partitioning between crystal-plasticity and solution-transfer during folding/transposition of quartz may explain the common occurrence of layered quartz rocks, where individual layers show alternating c-axis fabrics with opposite asymmetries but a consistent GSF orientation. Such characteristics may reflect an earlier event of pervasive folding/transposition of a preexisting layering.     

Growth condition of quartz crystals at the Zhelannoe deposit in the Nether-Polar Urals: Evidence from fluid and solid inclusions

The topography of various faces of quartz crystals indicates that the late growth of rock crystals occurred at a relatively slow rate, by the layer by layer mechanism activated by screw dislocations. The capture mechanism of gas-liquid inclusions by quartz at the deposit is identified, and gas-liquid and solid inclusions are examined in various quartz populations. The temperature of the mineral-forming processes is evaluated from the homogenization temperatures of the inclusions. Distinct quartz populations are determined to be formed under similar physicochemical conditions, at temperatures no higher than 260°C, which increased from earlier to later quartz populations. The quartz veins were produced by solutions of sodic-hydrocarbonate composition. The geochemical environment in which mineral-forming processes occurred at the Zhelannoe deposit was generally poor in fluid, and the inclusions are dominated by water and usually contain no more than 10 wt % carbon dioxide, strongly subordinated amounts of nitrogen and carbon monoxide, and no identifiable methane amounts.