Dynamic condensation of water at crack tips in fused silica glass

Water molecules play a fundamental role in the physics of slow crack propagation in glasses. It is commonly understood that, during stress-corrosion, water molecules that move in the crack cavity effectively reduce the bond strength at the strained crack tip and, thus, support crack propagation. Yet the details of the environmental condition at the crack tip in moist air are not well determined. In a previous work, we reported direct evidence of the presence of a 100 nm long liquid condensate at the crack tip in fused silica glass during very slow crack propagation (10^?9–10^?10 m/s). These observations are based on in situ AFM phase imaging techniques applied on DCDC glass specimens in controlled atmosphere. Here, we discuss the physical origin of the AFM phase contrast between the liquid condensate and the glass surface in relation to tip-sample adhesion induced by capillary bridges. We then report new experimental data on the water condensation length increase with relative humidity in the atmosphere. The measured condensation lengths were much larger than what predicted using the Kelvin equation and expected geometry of the crack tip.     

Fabrication and thermal evolution of nanoparticles in SiO2 by Zn ion implantation

SiO₂ samples were implanted with 45 keV Zn ions at doses ranging from 5×10¹⁵ to 1.0×10¹⁷ ions/cm², and were then subjected to furnace annealing at different temperatures. Several techniques, such as ultra-violet–visible spectroscopy (UV–vis), grazing incidence X-ray diffraction spectroscopy (GXRD) and atomic force microscopy (AFM), have been used to investigate formation of nanoparticles and their thermal evolution. Our results clearly show that Zn nanoparticles could be effectively formed in SiO₂ at doses higher than 5×10¹⁶ ions/cm². The subsequent thermal annealing at oxygen ambient could induce the growth of Zn nanoparticles at intermediate annealing temperature range. While at temperature above 600 °C, Zn nanoparticles could be transformed into ZnO, or even Zn₂SiO₄ nanoparticles. The results have been tentatively discussed in combination with Zn diffusion and migration obtained by Rutherford backscattering spectroscopy (RBS) measurements.     

Hybrid observation of crystal growth using laser confocal microscope with atomic force microscope

We built up a hybrid microscope system that consists of an atomic force microscope (AFM) and a laser confocal microscope with differential interference contrast microscope (LCM-DIM) and investigated the combined imaging of a potassium dihydrogen phosphate (KDP) crystal surface and its growth. Using this integrated setup, we were able to approach a AFM cantilever tip to several-ten μm$\mathrm{\mu }\mathrm{m}$ crystals using an optical microscope with AFM and to observe steps with measuring the height using LCM-DIM/AFM. Evaluation of the accuracy of the setup was studied and resulted in less than 100 nm of the AFM tip accuracy using LCM-DIM/AFM. We also demonstrated an in-situ observation of a KDP crystal growth using LCM-DIM/AFM. The interference fringes at the cantilever and the movements of steps were simultaneously observed.     

Crack growth threshold in soda lime silicate glass: role of hold-time

Atomic force microscopy was used to examine the shapes of cracks and residual features left behind on the fracture surface after holding cracks at a stress-intensity factor below the fatigue threshold for soda lime silicate glass. After propagating a crack at a stress-intensity factor of K_I=0.37 MPa m^1/2, the crack was held either at K_I=0.24 MPa m^1/2, or K_I=0.1 MPa m^1/2 for periods ranging from 1 h to approximately 200 h. Cracks held at the higher K_I left featureless lines on the fracture surface. Becoming more pronounced as the hold-time increased, these lines marked the position of a corrosive notch that formed during the hold period. At about 30 nm from the crack tip, the crack surface displacement decreased reaching zero at the crack tip. The crack tip shape was that of an ogee arch. At the lower hold valued of K_I, crack bifurcation occurred during which the crack became wavy, part of the crack propagating into the crack plane, part out of the crack plane when the crack was repropagated. A smaller crack tip displacement was observed for these cracks. Results of this study are believed to be a consequence of corrosion of the fracture surface caused by a basic solution formed when alkali ions (Na⁺ and K⁺) at the crack tip exchange with hydrogen ions in solution.     

Sodium diffusion in boroaluminosilicate glasses

Understanding the fundamentals of alkali diffusion in boroaluminosilicate (BAS) glasses is of critical importance for advanced glass applications, e.g., the production of chemically strengthened glass covers for personal electronic devices. Here, we investigate the composition dependence of isothermal sodium diffusion in BAS glasses by ion exchange, inward diffusion, and tracer diffusion experiments. By varying the [SiO₂]/[Al₂O₃] ratio of the glasses, different structural regimes of sodium behavior are accessed. We show that the mobility of the sodium ions decreases with increasing [SiO₂]/[Al₂O₃] ratio, revealing that sodium is more mobile when it acts as a charge compensator to stabilize network formers than when it acts as a creator of non-bridging oxygens on tetrahedrally-coordinated silicon and trigonal boron. The impacts of both the addition of iron and its redox state on the sodium diffusivity are explored in terms of the structural role of ferric and ferrous ions. By comparing the results obtained by the three approaches, we observe that both the tracer Na diffusion and the Na–K interdiffusion are significantly faster than the Na inward diffusion. The origin of this discrepancy could be attributed to the fact that for sodium inward diffusion, the charge compensation for electron holes is a rather slow process that limits the rate of diffusion.     

Crystallization Kinetics of NaCl in Multicomponent Solutions

Experimental results of solubility and growth kinetics measurements of sodium chloride crystals in multicomponent systems at 303 K are given. The effect of several solutes in elevated concentrations on the growth and dissolution kinetics is analysed on volume diffusion and surface integration steps: While the diffusion of ions within the solution decreases by the presence of foreign ions, the integration resistance can increase (mobile or immobile adsorption of foreign ions) or may even be reduced in some cases (due to a decreased surface energy).     

Fracture-induced luminescence in Alkali Halides

Crack propagation in dielectric solids is connected with many structural and electronic excitation processes. In order to obtain some information on the elementary excitation mechanism, crack velocity and fracture-induced luminescence in LiF and NaF (as received; doped; X-irradiated) under high vacuum conditions were correlated. Time-resolved crack velocity measurements revealed the usually discontinuous manner of crack propagation; maximum crack velccities of 3800 m/s (LiF) and 3000 m/s (NaF) were observed. Luminescence excitation in the X-irradiated samples occured at slow crack motion i.e. for increased plastic processes in the crack tip zone. The luminescence was explained by the recombination of stabilized radiation defects (F-centres and interstitial halogen atoms) involving a radiative exciton decay. The recombination is triggered by the crack via mobilization of the recombination partners by dislocations or lattice deformation processes.     

Fracture toughness evaluation of precursor-derived Si–C–N ceramics using the crack opening displacement approach

Difficulties in the fabrication of representative test specimens and in the application of suitable test procedures e.g., in the measurement of the test parameters viz., load, crack length etc., have so far limited the intrinsic fracture mechanical characterization of the precursor-derived ceramics (PDC). The present work reports the evaluation of the crack tip toughness (K_I0) of Si–C–N ceramics, using the novel crack opening displacement (COD) approach. The fully dense PDC test specimens synthesized from a poly(ureamethylvinyl)silazane precursor covered material structures ranging from partly organic amorphous to inorganic nano-crystalline states. Critically loaded cracks were achieved using either a special loading fixture or with Vickers indentation. Crack tip CODs were measured with the atomic force microscopy (AFM). Fractography of the fracture surfaces were performed using topographic, frictional and phase contrast AFM. The measured K_I0 values ranged from 0.6 to 1.2 MPa m^1/2. The net change in crack resistance was affected by the stripping of OFC-hydrogen atoms in the amorphous materials and by the segregated turbostratic graphite phase in the phase-separated materials. Nano-scale crack deflection observed even in the amorphous materials indicated the presence of structural and compositional inhomogeneities within the amorphous network.     

Post UV irradiation annealing of E′ centers in silica controlled by H2 diffusion

We investigate the isothermal annealing of E′ centers generated by UV photons (266 nm) of a pulsed Nd:YAG laser in two natural silica types differing for their OH content. Electron spin resonance and absorption spectra recorded at room temperature at different delays from the laser exposure evidenced a partial reduction of E′ centers, more pronounced in the wet silica. These post irradiation kinetics complete within 10⁵ s, regardless the silica type, and they are consistent with a diffusion limited reaction between the E′ centers and the molecular hydrogen H₂. Analysis of our data is done by theoretical fits using the Waite's equation and compared with the H₂ diffusion parameters reported in literature. Finally, the interplay between the under radiation generation and the post irradiation annealing of E′ centers was investigated through repetitive laser exposures, which evidenced the higher resistance of wet silica to induced laser damage.     

Distributions of copper and CuBr in CuBr nanocrystallite-dispersed glasses prepared by copper staining

CuBr nanocrystallite-dispersed glasses were prepared by incorporation of copper into bromide ion-containing borosilicate glass using the technique of copper staining. The copper ion incorporation process was mainly controlled by ionic diffusion from the surface to the interior of the glass. The depth profiles of Cu and CuBr concentration were examined by energy dispersive X-ray analysis and by reference to the change in absorption intensity assigned to the CuBr exciton band along the depth. While the Cu concentration was found to decrease monotonically, the CuBr concentration profile showed a maximum at a distance of 10-50 μm from the glass surface. Although the depth reached by the copper ions became greater with increasing heat-treatment time, the depth at which CuBr was precipitated was found to be saturated. This means that regions were found in the glasses in which no CuBr crystallites precipitated, although migration of Cu ions to these regions had taken place.     

Solutal convection around growing protein crystals and diffusional purification in Space

Convective and diffusional mass transport to an isolated crystal growing from solution, with slow linear interface kinetics, is considered analytically as a generic scaling model. We focus on the interface kinetics which is slow as compared to the diffusion mass transport which is typical of protein crystal growth. Independently, full-scale numerical solutions of transport equations around a cylindrical crystal, at the center of the bottom of a cylindrical cell filled with the solution, are found. The two approaches give results that agree over a wide range of parameters, providing dimensionless relationships that allow predictions of the contribution of convection and diffusion to mass transport. Requirements for microgravity level in Space experiments to achieve diffusional mass transport are estimated on the basis of these relationships. Coefficients of impurity distribution between a growing crystal and its solution, under the influences of convection and diffusion around the crystal, were numerically evaluated as functions of time. The results provide further support for the hypothesis concerning the role of the impurity depletion zone in the purification of a growing crystal. They also reveal that in general, the impurity distribution within the crystal is not homogeneous due to convection. The effects of various factors on growth kinetics and crystal purity are considered.     

Crystallization habit of calcium carbonate in presence of sodium dodecyl sulfate and/or polypyrrolidone

The synthesis of calcium carbonate (CaCO₃) crystals from aqueous solutions containing sodium dodecyl sulfate (SDS), poly(N-vinyl-1-pyrrolidone) (PVP) or SDS/PVP complexes has been performed through a slow titration method. It was found that aragonite and calcite coexisted in the prepared crystals. The formation of aragonite in the precipitation systems without magnesium ions indicates that at ambient temperature ca. 26.0°C, initially formed amorphous CaCO₃ could also transfer into aragonite in the sedimentary phase, which indicates the controlling factor of organic additives in the nucleation and growth process of CaCO₃ crystals. The appearance of hexagonal crystals in the suspensible phase confirmed the hexagonal crystallization cell of vaterite, and revealed the colloidal-dispersion function of the SDS/PVP complex in the crystallization process of CaCO₃.     

Temperature fluctuations in a LiNbO3 melt during crystal growth

The synthesis of calcium carbonate (CaCO₃) crystals from aqueous solutions containing sodium dodecyl sulfate (SDS), poly(N-vinyl-1-pyrrolidone) (PVP), or SDS/PVP complexes has been performed through a slow titration method. It was found that aragonite and calcite co-existed in the prepared crystals. The formation of aragonite in the precipitation systems without magnesium ions indicates that at ambient temperature ca. 26.0°C, initially formed amorphous CaCO₃ could also transfer into aragonite in the sedimentary phase, which indicates the controlling factor of organic additives in the nucleation and growth process of CaCO₃ crystals. The appearance of hexagonal crystals in the suspensible phase confirmed the hexagonal crystallization cell of vaterite, and revealed the colloidal-dispersion function of the SDS/PVP complex in the crystallization process of CaCO₃.     

Densification modeling of fused silica under nanoindentation

Fused silica is the reference material used for estimating the area function of nanoindenter tips. Despite being a fundamental step in nanoindentation, little has been done to study its deformation. Under a complex state of stress during indentation, fused silica densifies pointing out that the hydrostatic stress contributes to its yielding. A linear Drucker–Prager model is successfully employed to describe fused silica deformation. Real tip geometry obtained from Atomic Force Microscopy (AFM) is utilized to numerically simulate the area calibration process. Our results indicate a significant discrepancy between the tip area input into our simulation and the one obtained by the calibration process. This implies that the estimated area is not an intensive property of the indenter tip but a convolution of the indenter geometry by the fused silica deformation characteristics and as such may produce erroneous values when used on other materials.     

Hydration of soda-lime glass

The hydration of soda-lime glass is studied using resonant nuclear reactions to measure the hydrogen and sodium profiles of hydrated glasses. The rate of growth of the surface layer of hydrated glass is initially proportional to the square root of time as is characteristic of diffusion controlled processes. After longer exposure a steady-state hydration profile is observed, which indicates that in addition to the diffusion controlled reaction there is a slow etching of the glass surface. The measured hydration profiles are discussed in relationship to the Doremus model of interdiffusing ions, which is found to be in good agreement with the data. This model is also discussed in relationship to measured hydration profiles of vacuum heated samples of hydrated glass.     

Sub-critical crack growth rate of soda-lime-silicate glass and less brittle glass as a function of fictive temperature

Sub-critical crack growth rates of soda-lime-silicate glass and less brittle glass with different fictive temperatures were compared using the DCDC method under both dry and humid atmospheres in order to investigate the origin of the unique mechanical features of the less brittle glass developed by Ito and his collaborators. In both dry and humid atmospheres, the crack velocity of the soda-lime-silicate glass was slower than that of the less brittle glass. For both glasses, the glass sample with higher fictive temperature showed a slower crack growth rate under both dry and humid atmospheres. These observations can be explained by the tendency for the plastic flow at the crack tip; the soda-lime-silicate glass is expected to show easier plastic flow under tension than the less brittle glass, and also the samples with higher fictive temperatures are expected to show easier plastic flow, leading to greater fracture toughness, K_IC, and slower crack growth rate.     

Crack path instabilities in DCDC experiments in the low speed regime

We studied the low speed fracture regime (10⁻⁴-10⁻⁹ m s⁻¹) in different glassy materials (soda-lime glass, glass ceramics) with variable but controlled length scale of heterogeneity. The chosen mechanical system enabled us to work in pure mode I (tensile) and at a fixed load on double cleavage drilled compression specimen. The internal residual stresses of studied samples were carefully relaxed by appropriate thermal treatment. By means of optical and atomic force microscopy techniques fracture surfaces have been examined. We have shown for the first time that the crack front line underwent an out-of-plane oscillating behavior as a result of a reproducible sequence of instabilities. The wavelength of such a phenomenon is in the micrometer range and its amplitude in the nanometer range. These features were observed for different glassy materials providing that a typical length scale characterizing internal heterogeneities was lower than a threshold limit estimated to few nanometers. This effect is the first clear experimental evidence of crack path instabilities in the low speed regime in a uniaxial loading experiment. This phenomenon has been interpreted by referring to the stability criterion for a straight crack propagation as presented by Adda-Bedia et al. [Phys. Rev. Lett. 76 (1996) 1497].     

Direct AFM observations of impurity effects on a lysozyme crystal

Impurity effects on the growth of tetragonal lysozyme crystals have been studied using in situ atomic force microscopy. Commercially available hen egg white lysozyme was characterized by sodium dodecyl sulfate polyacrylamide gel electrophoresis with silver staining, and purified by re-crystallization and successive high pressure liquid chromatography. On the (1 1 0) crystal surface, there was no significant difference in morphology between crystals grown in commercial and in purified solutions. On the (1 0 1) surface, however, a large number of small particles were found when the crystal was grown in the commercial solution, while the surface grown in the purified solution was quite smooth. Among the typical residual impurities contained in commercial lysozyme, only covalently bound lysozyme dimer yielded such particles. From measurements of particle separation and an estimate of the critical nucleation size, we infer that the particles reduced the step velocity according to the mechanism described by Cabrera et al. [N. Cabrera, D.A. Vermilyea, in: R.H. Doremus et al. (Eds.), Growth and Perfection of Crystals, 1958, P. 393].     

Sodium tracer diffusion in glasses of the type (CaO·Al2O3)x(2 SiO2)1−x

Tracer diffusion coefficients of the radioactive isotope Na-22 were measured in glasses of the type (CaO·Al₂O₃)_x(2 SiO₂)_1−x to study the diffusion of sodium as a function of glass composition, x, temperature and initial water content. The diffusion of Na-22 in glasses diffusion-annealed in dry air can always be well described by a single tracer diffusion coefficient, but sometimes not in samples annealed in common air. It was found that the sodium tracer diffusion coefficient decreases by about six orders of magnitude when the glass composition x changes from 0 to 0.75 at 800 °C. The temperature dependence of the diffusion of sodium seems to decrease as the silica content increases. Variations of the initial water content in some of the glasses investigated did not very significantly influence the rate of the tracer diffusion of sodium.