research papers
Deciphering the intrinsic dynamics from the beam-induced atomic motions in oxide glasses
aESRF – The European Synchrotron, 71 avenue des Martyrs, 38000 Grenoble, France
*Correspondence e-mail: chushkin@esrf.fr
Probing the microscopic slow structural relaxation in oxide glasses by X-ray photon correlation spectroscopy (XPCS) revealed faster than expected dynamics induced by the X-ray illumination. The fast beam-induced dynamics mask true slow structural relaxation in glasses and challenges application of XPCS to probe the atomic dynamics in oxide glasses. Here an approach that allows estimation of the true 2, GeO2 and B2O3 glasses, it is concluded that the beam-induced dynamics show rich behavior depending on the sample.
of the sample in the presence of beam-induced dynamics is presented. The method requires two measurements either with different X-ray beam intensities or at different temperatures. Using numerical simulations it is shown that the slowest estimated true is limited by the accuracy of the measured relaxation times of the sample. By analyzing the reported microscopic dynamics in SiOKeywords: XPCS; glasses; beam effect.
1. Introduction
Upon rapid cooling of a liquid below its melting temperature the liquid may enter into a supercooled liquid metastable state by avoiding crystallization (Doremus, 1994; Varshneya & Mauro, 2019). Further cooling increases viscosity and transforms the liquid into a glass at the temperature Tg. Glasses are amorphous solids and their structural relaxation is too slow to be observed at the laboratory time scale. At Tg the of a liquid η is 1012 Pa s and the structural τ is 100 s by convention. According to Angell (1985), liquids can be classified as `strong' and `fragile'. The viscosity of `strong' liquids follows the Arrhenius behavior upon cooling while `fragile' liquids are characterized by non-Arrhenius character. There are several theories that describe the viscosity of supercooled liquids upon cooling (Doremus, 1994; Avramov, 2005; Dyre, 2006; Ojovan, 2008) but a unified microscopic picture is still missing. During the no noticeable transformation of disordered structure is observed yet the dynamic S(q, t) shows a rich behavior that reflects the dramatic slowing down of the molecular motions (Pusey & van Megen, 1987; van Megen et al., 1992; Horbach & Kob, 2001). Therefore study of the microscopic relaxation processes of the glass formation is central to its understanding.
Dynamic structure factors can be measured using scattering experiments. In recent years X-ray photon correlation spectroscopy (XPCS) has been developed as a powerful tool to probe the structural et al., 2009; Ruta et al., 2012). In XPCS one measures the temporal intensity autocorrelation function that relates to the intermediate scattering function (dynamic structure factor) (Grübel et al., 2008). Thus the microscopic nature of the structural relaxation can be investigated. XPCS applied to metallic glasses revealed the dynamical transition at Tg when the stretched in the supercooled liquid state changes to a compressed exponential behavior in the glass (Ruta et al., 2012). Although the mechanism responsible for the change is not explained, it is a very clear indicator of the and was observed in numerous studies in colloidal (Kwaśniewski et al., 2014) and metallic glasses (Ruta et al., 2012).
at the atomic length scale (LeitnerOxide glasses such as SiO2, GeO2, B2O3 and their derivatives are an important class of materials from industrial and scientific points of view. Pure silica, germania and boron trioxide are network glasses and their structures are built from the tetrahedron (silica and germania) or linked boroxol groups randomly arranged in a three-dimensional network (Zachariasen, 1932). The connection of the structural units in the random network is assured by the bridging oxygen atoms. In this respect oxide glasses are fundamentally different from metallic glasses where the atomic interactions are isotropic and hard-sphere like. Moreover, the network glass-formers are `strong' liquids characterized by a high kinetic fragility index (100) while metallic glass-formers have a smaller value (20) (Wang et al., 2004).
Recent investigations of microscopic dynamics in oxide glasses by XPCS revealed faster than expected relaxation times in a deep glassy state related to the beam-induced effect (Ruta et al., 2017; Dallari et al., 2019; Pintori et al., 2019; Holzweber et al., 2019). In all of the above cases (Ruta et al., 2017; Dallari et al., 2019; Pintori et al., 2019; Holzweber et al., 2019) the X-ray probe interacts with the sample and causes artificial structural relaxations that otherwise should not occur in the sample. It was clearly identified that the measured relaxation times scale inversely with the intensity of the X-ray beam (Ruta et al., 2017; Pintori et al., 2019; Holzweber et al., 2019) and that the sample dynamics and beam-induced dynamics are independent processes (Pintori et al., 2019). Although no visible structural damage was observed during the XPCS measurements, the reported beam-induced dynamics precludes the studies of the true microscopic dynamics in oxide glasses and limits the application of XPCS. The problem will become even more severe with the 100-fold increase in coherent expected from the synchrotron source upgrade (Raimondi, 2016) and necessitates further investigation. In this work we address the above issue. Based on the mathematical and numerical analysis we show possible routes to estimate the true sample dynamics from the measured values influenced by the beam effect. The results show that the slowest possible estimated time depends on the accuracy of the measurements.
2. Mathematical analysis
The measured quantity in XPCS is a temporal intensity I(q, t) autocorrelation function, g(2)(q,t) = , where 〈…〉 denotes the time average over t0 and q is the magnitude of the scattering vector. g(2)(q, t) is related to the intermediate scattering function f(q, t) = S(q, t)/S(q) via the Siegert relation g(2)(q, t) = 1 + C[f(q, t)]2, and C is a contrast that depends on the experimental setup and sample properties. The intermediate scattering function describes the relaxation process in space and time, f(q,t) = with the characteristic τ, and β defines the shape of the decay. In the supercooled liquid state, β < 1, and in the metallic (Ruta et al., 2012) and some oxide (Ruta et al., 2017) glasses, β > 1. τ is the microscopic structural of the system and depends on the scattering vector q and the temperature T. For `strong' glass-formers the temperature dependence of the sample τs(T) can be described by the Arrhenius behavior = , where τ0 is a constant, Ea is an activation energy and kB is the Boltzmann constant.
We consider that when beam-induced dynamics occur in a sample, owing to X-ray illumination with F, the measured τ(F, T) is composed of two contributions: the intrinsic dynamics of the sample τs(T) and the beam-induced dynamics τind(F),
This relation can describe the experimental observations of Pintori et al. (2019) in B2O3 glass. The beam-induced assumed to be temperature independent, is inversely proportional to the average (Ruta et al., 2017; Pintori et al., 2019; Holzweber et al., 2019),
where P is a proportionality constant. It depends on a sample's linear X-ray μ and sample thickness L via P = (Pintori et al., 2019; Holzweber et al., 2019). P0 gives a number of absorbed photons that leads to a 1/e decay of the intermediate scattering function in a given sample. For the moment we considered P to be temperature independent.
Then equation (1) can be rewritten in the following form,
When we have two or more measurements of τ(F, T) at different F, we can fit it with a simple linear model y = b + ax. Then the intercept b provides an estimate of the relaxation rate of the sample 1/τs(T). This is the basic principle used in the proposed approach but its application is not trivial as we shall see below.
Based on the above principle we can consider two practical cases. The first: at low temperatures, in the deep glassy state, τs(Tlow) ≫ τind(F) and we can assume that the measured is dominated by the beam-induced effect: τ(F, Tlow) = τind(F). Conversely, at high temperatures, above Tg, and the measured is close to the true sample dynamics: τ(F, Thigh) = τs(Thigh). From the above asymptotic behavior we can envisage measuring the at low temperature and use τind(F) = τ(F, Tlow) for estimating the sample dynamics in the intermediate range near Tg using
where τind(F) = τ(F, Tlow). Assuming that τind(F) is temperature independent we can estimate it by measuring the dynamics at low temperature and then use this value to estimate the sample dynamics around Tg. For SiO2, GeO2 and B2O3, room temperature can be considered as low enough.
The second case: when the temperature independence of τind might not be valid then we can exploit the fact that the beam-induced effect is a linear function of the F, and by performing measurements using only two different fluxes one can estimate the true sample To accomplish the estimation we must know the ratio f = F1/F2 (F1 > F2, f > 1) between two different fluxes used, then it is easy to show that the sample can be obtained by
The equations (4) and (5) suggest two ways to estimate the sample from measurements. In principle, even in a deep glassy state when the true sample is very long to measure during the experiment, the dynamics can still be extracted from the measured beam-induced times. In spite of this interesting possibility, in practice this might be difficult to attain. The accuracy of the measurements imposes the limits on the reliable time estimations.
3. Numerical simulations
To study the effect of noise on the estimation of the sample σ = 1% of the mean value for τ(F, T). The temperature dependence of the sample τs(T) was described by the using parameters for Ea of B2O3 glass (Ojovan, 2008) and adjusting τ0 to match τs(Tg) = 100 s (Tg = 580 K) (Ojovan, 2008). We covered a temperature range across the region below and above Tg. The ratio f was fixed to 10 and τind(F1) to 20 s. Using equation (1) we calculated τ(F, T) adding the noise (red curve shown in Fig. 1). Applying equation (3) to 100 curves of τ(F, T) with Gaussian noise σ of 1% we obtained an estimation of τs(T) displayed by the gray circles in Fig. 1. The blue squares are estimated average values. The estimation follows the expected behavior (blue curve) up to an upper limit (black dash-dot line) after which the estimated value flattens.
we performed numerical simulations. We modeled the experimental noise using a Gaussian distribution with a relative standard deviationThe flattening results from the behavior of the relative variance that can be calculated using the following expression,
where the same relative standard deviation σ is assumed for τind(F) and τ(F, T). At low temperatures τ(F, T) asymptotically approaches τind and σs diverges. Adopting a 3σ criterion that τind − τ(F, T) ≥ 3σ[τind + τ(F, T)] and setting τind − τ(F, T) = 6στ(F, T) into equation (4) we can estimate the upper limit as = . The upper limits for σ = 1% and 10% are drawn in Fig. 1 for comparison.
Now we consider the second case when two measurements with different fluxes are performed at constant temperature. Such a case has an advantage because it can be applied when the beam-induced dynamics might be temperature dependent. The simulated curves (red and dashed green) are shown in Figs. 2 and 3. At each temperature we calculated 100 points (gray circles) corresponding to the normally distributed noisy τ(F1, T) and τ(F2, T), both with σ = 1%. At high temperatures gray points are narrowly distributed and coincide with the theoretical value (blue line). At low temperatures we observe a wide distribution of the estimated and it deviates from the expected behavior (blue line). The blue squares are average values. At low temperatures the average values deviate from the expected time and saturate at a certain level. The black dash-dot line is the upper limit. The relative variance can be calculated using the following expression:
Similar to the previous case, using a 3σ criterion, fτ(F1, T) − τ(F2, T) ≥ 3σ[fτ(F1, T) + τ(F2, T)] and setting fτ(F1, T) − τ(F2, T) = 6σfτ(F1, T) into equation (5), we can estimate the upper limit as = .
These results show that, in practice, the sample τind or τ(F2, T) when it is measured with an accuracy of 1%}. In the near future, 100 times higher coherent is expected from the new diffraction-limited synchrotron sources (Raimondi, 2016). Higher coherent F will have two substantial impacts. A positive impact is an increase in the signal-to-noise ratio (SNR) of the correlation function g(2) according to the following equation (Lumma et al., 2000),
can be estimated reliably up to a certain time {approximately 16.6[1/(6 × 0.01)] times slower thanwhere Np is the number of pixels in the detector used and tacq is the acquisition time. For simplicity we consider the beam size, sample-to-detector distance, contrast C etc. to be constant. A negative consequence is that, when the F increases by 100 times, the beam-induced τ decreases by 100 times and hence so does t. Nevertheless, the SNR still improves by ten times when keeping the same tacq. In this condition the relative accuracy of the measured will improve by a factor of ten (from 1% to 0.1%) but the absolute values will decrease by a factor of 100. The calculation of this scenario is shown in Fig. 3. Here we kept τ(F2, T) = 200 s with σ = 1% and set f = 100 and τ(F1, T) = 2 s with σ = 0.1%. As one can see, the behavior is qualitatively identical to the previous case but the deviation from the sample occurs at a factor of two slower times. Thus, it is possible to estimate the sample time to be 30 times slower than τ(F2, T). This example shows that it is feasible to take advantage of the increase in coherent To obtain the most optimal estimation of the true sample within the available measurement time tacq one should use the same time tacq for both measurements and seek to work with the smallest σ; and f should be larger than 15.
4. Discussion
The analysis performed in this study relies on the decoupling of the beam-induced et al., 2017; Pintori et al., 2019) consider radiolysis as the main mechanism of the beam-induced dynamics. An absorbed X-ray photon excites electrons that leads to a transient break up of the atomic bonds (Griscom, 1985; Ziaja et al., 2015; Medvedev et al., 2015) and causes subsequent cooperative atomic rearrangements detected by XPCS. Such beam-induced non-thermal bond breaking produces relaxations similar to thermal viscous structural relaxations. The idea of bond breaking that leads to plastic deformation was used in a model of viscosity of vitreous silica (Mott, 1987). Several experiments report a connection between radiation-induced bond breaking and viscosity. Indeed, continuous electron irradiation of borosilicate glasses reduced the viscosity and led to fluidization due to non-thermal bond breaking (Ojovan et al., 2009). Moreover, the electron beam can be exploited for shaping nanoscale vitreous silica (Zheng et al., 2010). Recently, atomic rearrangements under e-beam illumination have even been imaged in two-dimensional vitreous silica by (Huang et al., 2013). Plastic deformation (radiation-enhanced viscosity) in amorphous materials has been reported during ion irradiation (Volkert & Polman, 1991) as well. Understanding the microscopic character of radiation-induced dynamics can be gained by XPCS.
from the true sample and its strong temperature dependence. It retrieves the sample dynamics without knowing the origin of the beam-induced effect. However, studying both dynamics is important for a better understanding of the problem and for application of oxide glasses in radiation-high industrial environments. This study addressed the first problem, and the latter one requires further investigation. Recent works (RutaBecause atomic rearrangements can be sensitive to local structure (Leitner et al., 2009) it is interesting to look at the length scale dependence of the structural relaxation under X-ray illumination. Previous study provides data of beam-induced as a function of the scattering vector (Ruta et al., 2017). In Fig. 4 we plot the of SiO2 and GeO2 glasses in reduced units τ(q)q2. This allows us to compare beam-induced microscopic dynamics with the well understood diffusion process in a where particles randomly move in a viscous liquid. For a dilute undergoing the reduced is inversely proportional to the D, τ(q)q2 = 1/D (Pusey, 1991). When the is high and the interaction between them is important, the reduced is proportional to the static S(q), τ(q)q2 ∝ S(q)/D (Pusey, 1991). Such behavior was observed in beam-induced dynamics of alkali borate glasses (Holzweber et al., 2019). Yet the data for silica and germania presented in Fig. 4 are markedly different from the above two scenarios. The reduced can be better described by a linear behavior τ(q)q2 = c + kq, where c and k are constants. The constant k depends on the incident X-ray while the parameter c is negative and similar for all three curves. The linear behavior and compressed shape of the (Ruta et al., 2017) can be associated with the superdiffusive and cooperative rather than diffusive atomic motions. In addition, the surprisingly negative intercept c, that gives a non-physical negative apparent could be a signature of plastic yielding (Volkert & Polman, 1991), in analogy to a Binghman plastic that contains a negative term to account for yielding. Yet this conjecture requires further study.
The central premise of the presented analysis is the linear dependence of the beam-induced 2, GeO2 and B2O3 glasses (Ruta et al., 2017; Pintori et al., 2019; Holzweber et al., 2019). The X-ray beam can induce a non-thermal relaxation rate at room temperature that would correspond to the thermal relaxation rate of a glass heated to near its temperature, thus hundreds of degrees points to a common origin (the role of the bridging oxygen). This suggests a similarity between X-ray induced and thermal transient bond breaking and subsequent bond reformation.
on the inverse of the incident that was reported in several experiments on SiOClearly, in multicomponent oxide glasses the real picture can be more complex. A new study of alkali borate glasses reported a deviation from the single linear behavior in (Rb2O)30(B2O3)70 glass (Holzweber et al., 2019). Alkali oxides are network modifiers – their presence in a network glass influences structure, viscosity, mechanical properties and temperature (Varshneya & Mauro, 2019; Greaves & Ngai, 1995). In particular, adding alkali oxides in B2O3 glass transforms trigonal BO3/2 into tetragonal BO4/2- structural units (Varshneya & Mauro, 2019), leads to microsegregation (Greaves & Ngai, 1995), formation of ion conduction channels (Greaves, 1985) and decoupling of ion mobility from glass-forming matrix (Varshneya & Mauro, 2019). Obviously a simple bond-breaking scenario is not complete and should be elaborated to describe the experimental observations. Moreover, for a new sample, measurements with several different fluxes are required to verify if a beam-induce effect is a linear or non-linear function of incoming flux.
5. Conclusions
The measurements of microscopic dynamics in oxide glasses by XPCS are inevitably affected by the beam-induced structural rearrangements that preclude determination of the true sample structural Tg. The observation of diffusive and superdiffusive microscopic behaviors of the beam-induced dynamics and deviation from the linear dependence on the incident in various oxide glasses calls for further studies.
at the atomic length scale. However, when beam-induced atomic motion is a linear function of the X-ray then, by performing two measurements, either at two different temperatures or with two different fluxes, it is possible to estimate the true sample in simple glasses up to a certain extent into the glassy state. This extent depends on the accuracy of the measured relaxation times. Therefore, the application of XPCS for the investigation of atomic dynamics in oxide glasses will largely benefit from the increase in precision of measuring the intermediate scattering function, and determination of the relaxation time and the shape parameter. Moreover, the described framework can be useful for developing a better understanding of non-linear beam-induced effects and many intriguing properties of oxide glasses and supercooled liquids aroundAcknowledgements
The author would like to thank Nikita Medvedev for insightful discussion on X-ray radiation damage and Theyencheri Narayanan for his critical reading of the manuscript and suggestions.
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