Crystallization Of Amorphous Solid Water Research Articles

Thermal desorption of H2O ice: from nanoscale films to the bulk

ABSTRACT The desorption properties of H2O films are investigated across a wide range of film thicknesses from 53 nanometres (nm) to 101 micrometres (μm) using a quartz-crystal microbalance (QCM) and temperature-programmed desorption. Three desorption stages are observed belonging to amorphous solid water (ASW), stacking disordered ice I (ice Isd), and hexagonal ice I (ice Ih). The desorption of ASW is only detectable for the ≥10 μm films and is separated from the ice I desorption by 10–15 K with an associated desorption energy of ∼64 kJ mol−1. The desorption energy of the 53-nm film was found to be near 50 kJ mol−1 as also noted in the literature, but with increasing film thickness, the desorption energy of ice I rises, reaching a plateau around 65–70 kJ mol−1. The reason for the increased desorption energy is suggested to be due to molecules unable to desorb due to the thick covering layer of H2O and possibly re-adsorption events. Before complete desorption of ice I at around 220 K for the 101 μm film, a two-stage ice I desorption is observed with the QCM for the ≥10 μm films near 200 K. This event corresponds to the desorption of ice Isd as corroborated by X-ray diffraction patterns collected upon heating from 92 to 260 K at ambient pressure. Cubic ice is not observed as is commonly stated in the literature as resulting from the crystallization of ASW. Therefore, ice Isd is the correct terminology for the initial crystallization product of ASW.

Rapid crystallization of amorphous solid water by porosity induction.

Rapid crystallization of amorphous solid water (ASW) is often associated with crystallization that initiates at random nucleation sites in the bulk and expands in all directions. In this work, by preparing sandwich films of acetonitrile (ACN) and ASW in the form of ACN@ASW and ASW@ACN in an ultrahigh vacuum (UHV), we demonstrate a new method for rapid crystallization of ASW via ACN diffusion-desorption induced porosity in the ASW matrix even in the window of 128-134 K, well below the normal crystallization temperature of 155 K. By placing an HDO (5% D2O in H2O) probe layer in ASW, we found that when ACN diffuses and desorbs through ASW, it induces ASW crystallization where the crystal grows both from the top and from the bottom simultaneously into the bulk. Crystallization kinetics and activation energy (Ea) for the formation of crystalline ice (CI) were evaluated using the Avrami equation and were compared with the previous reports. The evaluated Ea was ∼53 kJ mol-1, close to the Ea of crystal growth (47-56 kJ mol-1) and it suggested the absence of a nucleation process and supported rapid crystallization. Such occurrence of CI due to diffusion of ACN suggests a possible mechanism for the former's existence in many astrophysical environments.

Volatility of Amorphous Solid Water.

Amorphous solid water is probably the most abundant form of solid water in the universe. Its saturation vapor pressure and thermodynamic properties, however, are not well known. We have investigated the saturation vapor pressure over vapor-deposited amorphous ice at temperatures between 133 and 147 K using a novel experimental method. The new method determines the absolute vapor pressures and the sublimation rates by measuring the mass growth rates of ice-covered nanoparticles under supersaturated water vapor conditions. We find that the vapor pressure of amorphous solid water is up to a factor of 3 higher than that predicted by current parameterizations, which are based in part on calorimetric measurements. We demonstrate that the calorimetric measurements can be reconciled with our data by acknowledging the formation of nanocrystalline ice as an intermediate ice phase during the crystallization of amorphous ice. As a result, we propose a new value for the enthalpy of crystallization of amorphous solid water of Δ H = 2312 ± 227 J/mol, which is about 1000 J/mol higher than the current consensus. Our results shine a new light on the abundance of water ice clouds on Mars and mesospheric clouds on Earth and may alter our understanding of ice formation in the stratosphere.

Acid-Promoted Crystallization of Amorphous Solid Water

In this study, the effect of externally added hydrogen chloride (HCl) on the crystallization of amorphous solid water (ASW) has been examined. ASW films containing small amounts of HCl, which dissociated into H+ (excess protons) and Cl– ions, and having a thickness of 90–360 monolayers (ML) were prepared on a Pt(111) substrate under an ultrahigh vacuum environment. The location of HCl in the samples was varied by controlling the stacking sequence of H2O and HCl during the film growth. Crystallization kinetics of these samples were examined by conducting temperature-programmed desorption experiments and isothermal kinetic measurements with reflection–absorption infrared spectroscopy for the temperature range of 137–145 K. Crystallization behaviors of pure and NaCl-doped ASW films were also examined for comparison. The results indicated that the excess protons accelerated the crystallization of the ASW films, in contrast to the retardation effect of Na+. In the presence of 0.1 ML HCl, the overall activation energy of ASW crystallization was reduced from 63.4 kJ·mol–1 in the absence of HCl to 48.5 kJ·mol–1, which is close to the activation energy of crystal growth. The crystallization started near the location of HCl injection in the samples, regardless of whether it was the vacuum/ASW interface or the film interior. These observations indicated that the excess protons facilitated the nucleation process and changed the rate-limiting step of ASW crystallization from nucleation to growth. An explanation based on thermodynamics has been proposed, that is, the configurational entropy of the excess protons in ice likely reduces the free-energy barrier of nucleation for the acid-doped ASW samples.

The vapor pressure over nano-crystalline ice

Abstract. The crystallization of amorphous solid water (ASW) is known to form nano-crystalline ice. The influence of the nanoscale crystallite size on physical properties like the vapor pressure is relevant for processes in which the crystallization of amorphous ices occurs, e.g., in interstellar ices or cold ice cloud formation in planetary atmospheres, but up to now is not well understood. Here, we present laboratory measurements on the saturation vapor pressure over ice crystallized from ASW between 135 and 190 K. Below 160 K, where the crystallization of ASW is known to form nano-crystalline ice, we obtain a saturation vapor pressure that is 100 to 200 % higher compared to stable hexagonal ice. This elevated vapor pressure is in striking contrast to the vapor pressure of stacking disordered ice which is expected to be the prevailing ice polymorph at these temperatures with a vapor pressure at most 18 % higher than that of hexagonal ice. This apparent discrepancy can be reconciled by assuming that nanoscale crystallites form in the crystallization process of ASW. The high curvature of the nano-crystallites results in a vapor pressure increase that can be described by the Kelvin equation. Our measurements are consistent with the assumption that ASW is the first solid form of ice deposited from the vapor phase at temperatures up to 160 K. Nano-crystalline ice with a mean diameter between 7 and 19 nm forms thereafter by crystallization within the ASW matrix. The estimated crystal sizes are in agreement with reported crystal size measurements and remain stable for hours below 160 K. Thus, this ice polymorph may be regarded as an independent phase for many atmospheric processes below 160 K and we parameterize its vapor pressure using a constant Gibbs free energy difference of (982 ± 182) J mol−1 relative to hexagonal ice.

Communication: Distinguishing between bulk and interface-enhanced crystallization in nanoscale films of amorphous solid water.

The crystallization of amorphous solid water (ASW) nanoscale films was investigated using reflection absorption infrared spectroscopy. Two ASW film configurations were studied. In one case the ASW film was deposited on top of and capped with a decane layer ("sandwich" configuration). In the other case, the ASW film was deposited on top of a decane layer and not capped ("no cap" configuration). Crystallization of ASW films in the "sandwich" configuration is about eight times slower than in the "no cap." Selective placement of an isotopic layer (5% D2O in H2O) at various positions in an ASW (H2O) film was used to determine the crystallization mechanism. In the "sandwich" configuration, the crystallization kinetics were independent of the isotopic layer placement whereas in the "no cap" configuration the closer the isotopic layer was to the vacuum interface, the earlier the isotopic layer crystallized. These results are consistent with a mechanism whereby the decane overlayer suppresses surface nucleation and provide evidence that the observed ASW crystallization in "sandwich" films is the result of uniform bulk nucleation.

Porosity effects on crystallization kinetics of amorphous solid water: Implications for cold icy objects in the outer solar system

We have investigated the effects of porosity on the crystallization kinetics of amorphous solid water (ASW). Porosity in ASW films, condensed from the vapor phase at varying incidences at 10K, was characterized using ultraviolet-visible interferometry and quartz crystal microgravimetry. The films were heated to crystallization temperatures between 130 and 141K, resulting in partial pore compaction. The isothermal phase transformation was characterized using transmission infrared spectroscopy to monitor the time evolution of the 3.1-µm OH stretch absorption band. We find that ASW crystallization unfolds in two distinct stages. The first stage, responsible for ∼10% transformation, is initiated from nucleation at the external surface. The dominant second stage begins with nucleation at the internal pore surfaces and completes the transformation of the film at a faster rate compared to the first stage. A key finding is that porosity has major influence on crystallization kinetics; a film with five-times-higher porosity was observed to crystallize ∼15 times faster, compared to the less porous counterpart. We extrapolate our results to predict crystallization times for amorphous ices condensed on Europa's surface from plume sources, as recently observed by the Hubble Space Telescope.

Surface and bulk crystallization of amorphous solid water films: Confirmation of “top-down” crystallization

The crystallization kinetics of nanoscale amorphous solid water (ASW) films are investigated using temperature-programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS). TPD measurements are used to probe surface crystallization and RAIRS measurements are used to probe bulk crystallization. Isothermal TPD results show that surface crystallization is independent of the film thickness (from 100 to 1000 ML). Conversely, the RAIRS measurements show that the bulk crystallization time increases linearly with increasing film thickness. These results suggest that nucleation and crystallization begin at the ASW/vacuum interface and then the crystallization growth front propagates linearly into the bulk. This mechanism was confirmed by selective placement of an isotopic layer (5% D2O in H2O) at various positions in an ASW (H2O) film. In this case, the closer the isotopic layer was to the vacuum interface, the earlier the isotopic layer crystallized. These experiments provide direct evidence to confirm that ASW crystallization in vacuum proceeds by a “top-down” crystallization mechanism.

Interactions of phenylglycine with amorphous solid water studied by temperature-programmed desorption and photoelectron spectroscopy

Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) have been employed to study the interactions of phenylglycine (PheGly) with amorphous solid water (ASW) nanolayers (10–50ML). First, the adsorption and growth of PheGly layers on an AlOx/NiAl(110) surface have been examined. After that, mixed PheGly–ASW layers have been grown on the alumina surface at 110K. Alternatively, PheGly molecules (from submonolayer to multilayer coverages) have been deposited on top of the ASW surfaces. In mixed PheGly–ASW nanolayers the PheGly phase displays hydrophobic behavior and accumulates near the surfaces of the films, while top-deposited PheGly wets the ASW films forming closed overlayers at low coverages. H2O desorption from the PheGly–ASW films is strongly influenced by the PheGly molecules, i.e., the crystallization of ASW is partially inhibited in the vicinity of the amino acid and a lower desorption temperature of H2O molecules than from pure ASW layers was detected. Thicker PheGly overlayers on ASW provide a kinetic restriction to H2O desorption from the underlying ASW layers until the PheGly molecules become mobile and develop pathways for water desorption at higher temperatures. The results are discussed with respect to the previously obtained data for glycine–ASW layered systems. It has been demonstrated that the substitution of the hydrogen atom in glycine with a phenyl group does not lead to detectable changes in the pathways of ASW desorption. However, desorption of PheGly differs from the desorption of glycine from the similarly structured glycine–ASW nanolayers. The differences are interpreted in terms of adsorbate–adsorbate and adsorbate–substrate interactions.

The release of trapped gases from amorphous solid water films. I. “Top-down” crystallization-induced crack propagation probed using the molecular volcano

In this (Paper I) and the companion paper (Paper II; R. May, R. Smith, and B. Kay, J. Chem. Phys. 138, 104502 (2013)), we investigate the mechanisms for the release of trapped gases from underneath amorphous solid water (ASW) films. In prior work, we reported the episodic release of trapped gases in concert with the crystallization of ASW, a phenomenon that we termed the "molecular volcano." The observed abrupt desorption is due to the formation of cracks that span the film to form a connected pathway for release. In this paper, we utilize the "molecular volcano" desorption peak to characterize the formation of crystallization-induced cracks. We find that the crack length distribution is independent of the trapped gas (Ar, Kr, Xe, CH4, N2, O2, or CO). Selective placement of the inert gas layer is used to show that cracks form near the top of the film and propagate downward into the film. Isothermal experiments reveal that, after some induction time, cracks propagate linearly in time with an Arrhenius dependent velocity corresponding to an activation energy of 54 kJ∕mol. This value is consistent with the crystallization growth rates reported by others and establishes a direct connection between crystallization growth rate and the crack propagation rate. A two-step model in which nucleation and crystallization occurs in an induction zone near the top of the film followed by the propagation of a crystallization∕crack front into the film is in good agreement with the temperature programmed desorption results.

The release of trapped gases from amorphous solid water films. II. “Bottom-up” induced desorption pathways

In this (Paper II) and the preceding companion paper (Paper I; R. May, R. Smith, and B. Kay, J. Chem. Phys. 138, 104501 (2013)), we investigate the mechanisms for the release of trapped gases from underneath amorphous solid water (ASW) films. In Paper I, we focused on the low coverage regime where the release mechanism is controlled by crystallization-induced cracks formed in the ASW overlayer. In that regime, the results were largely independent of the particular gas underlayer. Here in Paper II, we focus on the high coverage regime where new desorption pathways become accessible prior to ASW crystallization. In contrast to the results for the low coverage regime (Paper I), the release mechanism is a function of the multilayer thickness and composition, displaying dramatically different behavior between Ar, Kr, Xe, CH4, N2, O2, and CO. Two primary desorption pathways are observed. The first occurs between 100 and 150 K and manifests itself as sharp, extremely narrow desorption peaks. Temperature programmed desorption is utilized to show that these abrupt desorption bursts are due to pressure induced structural failure of the ASW overlayer. The second pathway occurs at low temperature (typically <100 K) where broad desorption peaks are observed. Desorption through this pathway is attributed to diffusion through pores formed during ASW deposition. The extent of desorption and the line shape of the low temperature desorption peak are dependent on the substrate on which the gas underlayer is deposited. Angle dependent ballistic deposition of ASW is used to vary the porosity of the overlayer and strongly supports the hypothesis that the low temperature desorption pathway is due to porosity that is templated into the ASW overlayer by the underlayer during deposition.

Probing the interaction of amorphous solid water on a hydrophobic surface: dewetting and crystallization kinetics of ASW on carbon tetrachloride

Desorption of carbon tetrachloride from beneath an amorphous solid water (ASW) overlayer is explored utilizing a combination of temperature programmed desorption and infrared spectroscopy. Otherwise inaccessible information about the dewetting and crystallization of ASW is revealed by monitoring desorption of the CCl(4) underlayer. The desorption maximum of CCl(4) on graphene occurs at ~140 K. When ASW wets the CCl(4) no desorption below 140 K is observed. However, the mobility of the water molecules increases with ASW deposition temperature, leading to a thermodynamically driven dewetting of water from the hydrophobic CCl(4) surface. This dewetting exposes some CCl(4) to the ambient environment, allowing unhindered desorption of CCl(4) below 140 K. When ASW completely covers the underlayer, desorption of CCl(4) is delayed until crystallization induced cracking of the ASW overlayer opens an escape path to the surface. The subsequent rapid episodic release of CCl(4) is termed a "molecular volcano". Reflection absorption infrared spectroscopy (RAIRS) measurements indicate that the onset and duration of the molecular volcano is directly controlled by the ASW crystallization kinetics.

Crystallization of D 2O thin films on Ru(0 0 1) surfaces

The phase conversion of amorphous solid water (ASW) to crystalline ice (CI) has been investigated in the very thin ( ∼ 10 monolayers) film regime on a Ru(0 0 1) surface. We analyze the converted CI fraction with the Avrami model, and recognize that one-dimensional CI growth occurs, which can be contrasted to the three-dimensional CI growth generally established in the thick ( ≥ 50 monolayers) film regime. We evaluate activation energy for the ASW crystallization to be about 1.0 eV. We suggest that the ASW crystallization is not influenced by the substrate even near the substrate–ice interface.

The effect of the incident collision energy on the phase and crystallization kinetics of vapor deposited water films

Molecular beam techniques are used to grow water films on Pt(111) with incident collision energies from 5 to 205 kJ/mole. The effect of the incident collision energy on the phase of vapor deposited water films and their subsequent crystallization kinetics are studied using temperature programmed desorption and infrared spectroscopy. We find that for films deposited at substrate temperatures below 110 K, the incident kinetic energy (up to 205 kJ/mole) has no effect on the initial phase of the deposited film or its crystallization kinetics. Above 110 K, the substrate temperature does affect the phase and crystallization kinetics of the deposited films but this result is also independent of the incident collision energy. The presence of a crystalline ice template (underlayer) does affect the crystallization of amorphous solid water, but this effect is also independent of the incident beam energy. These results suggest that the crystallization of amorphous solid water requires cooperative motion of several water molecules.

Surface crystallization of amorphous solid water.

We demonstrate that the crystallization of thin, supported amorphous solid water layers is initiated at the water surface. This is concluded from the observation of sequential crystallization of amorphous water at the surface, in the bulk, and at the water-support interface. A surface nucleation model quantitatively reproduces the observed transformation kinetics at the three sites.

A new methodology and model for characterization of nucleation and growth kinetics in solids

Herein we describe a new experimental protocol and develop a corresponding kinetic model of phase change that together enable the decoupling of simultaneous nucleation and growth processes and quantification of their kinetics. Growth is effectively isolated from nucleation by dividing a phase transition into two isothermal stages: prenucleation, where product crystallites nucleate and grow concurrently, and growth, in which transformation is completed essentially entirely by the expansion of these “seed” grains. Using the model, the temperature dependence of growth may be extracted from converted fraction versus time data for specimens that are appreciably larger than the mean crystal grain size. Similarly, the growth velocity can be ascertained from thin films that exhibit thickness-dependent transition kinetics owing to geometric constraints imposed by the specimen size. The combination of grain growth kinetics and information derived from the transformation of unseeded materials then allows the subsequent calculation of the temperature dependence and absolute rates of nucleation. A preliminary assessment of this method (for the crystallization of amorphous solid water) indicates that the model captures the basic physics of “seeded” transformations and that the technique appears to be a viable method of quantifying simultaneous nucleation and growth in some solids.

Observation of crystallization of amorphous solid water under the conditions of secondary emission mass spectrometric experiments

A phenomenon of termination of sputtering of protonated water clusters (H2O)nH+ in low-temperature secondary emission mass spectrometric studies of solid water is observed in the temperature range of crystallization of amorphous solid water (ASW). In this range the mass spectra contained only H3O+, H2O+•, and OH+ ions. The following explanation of the phenomenon revealed is suggested: the heat supplied to the ASW sample by the bombarding particles is spent on initiation of an amorphous–crystalline transition within the condensed sample but not for the transfer of the sample matter to the gas phase. At the same time heat released on crystallization causes a local rise in temperature of the crystallizing sample surface, which enhances the rate of sublimation of ice. The resulting increased concentration of subliming water molecules over the sample surface is reflected in a growth of the abundance of H2O+• molecular-ion radical, produced by gas-phase ionization mechanism. The appearance of a set of low-mass peaks in the course of crystallization observed for some types of ASW samples is explained by the release of gases trapped in the ASW film during its growth.

Substrate induced crystallization of amorphous solid water at low temperatures

We show that N2 monolayer desorption from ice surfaces is a quantitative, highly sensitive method for following the surface crystallization kinetics at low temperatures. Vapor deposited water films on a crystalline ice substrate exhibit amorphous growth at temperatures below ∼110 K. The rate of crystallization for these amorphous films is dramatically accelerated compared to the rate of crystallization observed for the amorphous films deposited directly on Pt(111). We find that the crystalline ice substrate acts as a two-dimensional nucleus for the growth of the crystalline phase, thereby accelerating the crystallization kinetics.

Evidence for Molecular Translational Diffusion during the Crystallization of Amorphous Solid Water

Molecular diffusion in amorphous solid water is studied by measuring the extent of isotope exchange and mixing in vapor-deposited ultrathin films using temperature-programmed desorption. Our results indicate there is long-range translational diffusion that occurs concomitantly with the amorphous to crystalline ice phase transition. The apparent diffusivity estimated from these data is a factor of 106±1 greater than an Arrhenius extrapolation for diffusion in crystalline ice. This finding suggests that the amorphous material exhibits liquid-like translational diffusion prior to crystallization at temperatures near 155 K.

The dielectric behavior of vapor-deposited amorphous solid water and of its crystalline forms

The dielectric permittivity and loss of vapor-deposited amorphous solid water (ASW) have been measured for fixed frequencies of 1 and 10 kHz from 80 K to its crystallization temperature. Similar measurements have also been made on the cubic ice formed after the crystallization of ASW and the hexagonal ice formed on heating the cubic ice. The loss tangent shows a broad sub-Tg relaxation peak centered at about 100 K and an approach towards a plateau value which appears as a shoulder. The peak is attributed to thermally activated rotation of H2O molecules with one or two dangling OH groups on the surface of the pores of the microporous sample, and the shoulder to localized motions within the network structure. Sintering of the samples on thermal cycling between 77 and ≊120 K in vacuo causes the broad peak to vanish. With increase in temperature, above Tg, the loss tangent shows the emergence of the expected α-relaxation peak of a liquid at T&amp;gt;Tg, whose completion is terminated by the onset of crystallization to cubic ice at about the same temperature for 1 kHz and for 10 kHz measurements. Thereafter, crystallization becomes slower, thus allowing further observation of the low-temperature part of the α-relaxation peak. The dielectric loss of amorphous solid water at 80 K is nearly 20 times that of the cubic ice formed on its crystallization after heating to 193 K, and nearly 3.5 times higher at Tg. The dielectric loss of the cubic ice formed on crystallization tends towards a plateau value prior to rapidly increasing with increase in temperature, an evidence for a low temperature relaxation which vanishes on conversion to hexagonal ice. This relaxation indicates a remnant topologically disordered structure of intergranular water and/or stacking faults in cubic ice. Samples sintered by thermal cycling in vacuo to ≊120 K crystallized in one step, whereas those without prior thermal cycling crystallized in two steps to cubic ice. Annealing of the ASW at 130 K completely removes the broad peak at ≊100 K and reduces the magnitude of the β-relaxation process. Partial crystallization of ASW completely removes the β-relaxation process, which indicates either preferential crystallization at the local regions of high mobility in the amorphous matrix or a change in the structure of the amorphous phase during crystallization.