Cristian
Rodríguez-Tinoco
*ab,
Marzena
Rams-Baron
ab,
K. L.
Ngai
b,
Karolina
Jurkiewicz
ab,
Javier
Rodríguez-Viejo
c and
Marian
Paluch
ab
aInstitute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland. E-mail: cristian.rodriguez-tinoco@smcebi.edu.pl
bSilesian Center for Education and Interdisciplinary Research, 75 Pulku Piechoty 1A, 41-500 Chorzow, Poland
cGroup of Nanomaterials and Microsystems, Physics Department, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain
First published on 23rd January 2018
Secondary relaxations are fundamental for their impact in the properties of glasses and for their inseparable connection to the structural relaxation. Understanding their density dependence and aging behavior is key to fully address the nature of glasses. Ultrastable glasses establish a new benchmark to study the characteristics of secondary relaxations, since their enthalpy and density levels are unattainable by other routes. Here, we use dielectric spectroscopy at ambient and elevated pressures to study the characteristics of the secondary relaxation in ultrastable etoricoxib, reporting a 71% decrease in dielectric strength and one decade increase in relaxation time compared to the ordinary glass. Interestingly, we find an unprecedented connection between secondary and structural relaxations in ultrastable etoricoxib in exactly the same manner as in the ordinary glass, manifested through different properties, such as aging and devitrification. These results further support and extend the general validity of the connection between the secondary and structural relaxation.
There are several routes to produce glasses: liquid-quenching,4 cryo-milling5 or high-pressure quenching,6 among others. The discovery of ultrastable glasses (USG) by vapor deposition represents a milestone in glass research.7,8 By adjusting the deposition conditions (mainly deposition temperature and evaporation rate), it is possible to tune the properties of the glass produced, such as its kinetics, thermodynamic stability and density, over a wide range.9–11 The enthalpy of USG is equivalent to that of ordinary glasses (OG) having been aged for millions of years, such as amber.12 Recent experiments have suggested that the high mobility of molecules landing on the surface during deposition is responsible for the enhanced stability and density of USG.13,14 Some works have associated the surface mobility or the structural relaxation of ultrathin films with the primitive relaxation time, τ0 of the Coupling Model or equivalently the JG-β relaxation time τJG.15 Moreover, it was shown recently that the JG-β relaxation is a rate limiting factor of the growth of vapor deposited glasses.16 Therefore, it seems that there is a strong connection between some secondary relaxations persistent in the glassy state with the characteristics of USG, and the connection offers insight into the dynamics of USG and a new benchmark to test theories of glasses.
Recently, it was shown that the intensity of the JG-β relaxation process in vapor deposited glasses of toluene can be tuned by changing the deposition temperature during the growth process.17 A decrease of around 70% in the intensity of the secondary JG process was observed in the USG compared to the OG. Also, the relaxation time of the process was seen to be longer in the USG than in the OG. This observation agrees with the previous knowledge, according to which aging and lower cooling rates applied during the formation of OG can yield less intense and slower secondary relaxation processes.18–20 More recently, it was shown that glasses of etoricoxib prepared at high pressure exhibited a slower secondary relaxation process attributed to the measured higher density of the system.21 In this work, we study this secondary relaxation process observed in USG and OG of etoricoxib focusing on its dependence on temperature and pressure, and its connection with the structural relaxation in properties.
Dielectric measurements at elevated pressure were performed using an automatic high-pressure system (Unipress). The sample, out of contact with compression medium by means of a Teflon casing, was fixed to the pressure chamber filled with silicon oil. The temperature during the measurement was controlled by means of a closed-circuit cooler connected to the pressure chamber.
Dielectric data is fitted by the Havriliak–Negami (HN) equation,
In Fig. 2A we show the dielectric spectra of the USG and OG measured at different temperatures in the glassy state. The OG was obtained after annealing an USG at 340 K (Tg + 13 K) for 12 h (see details in the ESI†). Alternatively, the glass is brought up to 352 K and cooled down, or obtained directly after melting of crystalline etoricoxib. In all cases, the obtained results are the same. From the relaxation map in Fig. 2B, we first note at Tg that the secondary relaxation time of the OG does not match the primitive relaxation time of the coupling model, as expected for a conventional JG β-relaxation involving the motion of the entire molecule.2 Noticeably, while the fitting of the secondary relaxation using a single HN curve is satisfactory for the OG, for the USG only the peak near the maximum is well fitted. This may be an indication of the presence of the weak and unresolved JG β-relaxation at lower frequencies in the dielectric spectra (see ESI†). In the inset of Fig. 2A, we indicate the expected position of the primitive relaxation frequency, consistent with the JG β-relaxation hidden between the α-relaxation and the observed secondary relaxation. The existence of the unresolved JG β-relaxation in etoricoxib is suggested also by its presence in celecoxib, a very similar molecule.25 Its dielectric relaxation strength in celecoxib is very weak and it was barely resolved as a bump in the loss spectra in the glassy state. Thus, it is not surprising that the JG β-relaxation cannot be resolved in etoricoxib, especially if it is next to and dominated by the strong secondary relaxation observed. The latter has relaxation time changing from Arrhenius dependence in the glassy state to a stronger T-dependence in the liquid state (see details of these data in the ESI†). This is a characteristic of JG processes. As we shall show later, this secondary relaxation has significant pressure dependence and related to the pressure dependence of the structural relaxation. From the connection of the properties of the secondary relaxation with the structural relaxation, we identify it as another JG process,2 faster than the genuine JG β-process, and refer it as the JG γ-process. The exact nature of this secondary relaxation has to wait until its motion is fully characterized by other techniques. The relatively large size of the etoricoxib molecule suggests that the observed faster JG γ-process is not a relaxation of the entire molecule, reserved for the JG β-relaxation, but involves the motion of only a part of it where the dipole moment resides. Notwithstanding, its pressure and density dependences is like that of the JG β-relaxation, indicating that it is also connected to the structural relaxation.
Fig. 2 Secondary relaxation of USG and OG. (A) Dielectric loss of the secondary relaxation of USG (stars) and OG (squares), from 293 K (black) to 213 K (pink), each 20 K. In the inset, dielectric loss above Tg for the USG and transformed sample (liquid), indicating the position of the primitive relaxation, according to the coupling model. (B) Map of relaxation times for OG (red) and USG (black) etoricoxib glasses. The orange solid line corresponds to the VFT fit from τα.31 The dotted dark yellow line corresponds to the primitive relaxation time calculated from the CM and using the reported values of coupling parameters.31 The vertical dashed lines indicate the devitrification temperature at different conditions (OG, USG and OG at 400 MPa), measured at 10 K min−1. The blue horizontal line indicates the time value at which the extrapolation of the secondary relaxation time intersects the corresponding indicated devitrification temperature (C) intensity of the secondary process for the OG (and for the liquid, above Tg) and for the USG. |
From the data in Fig. 2, two observations can be immediately made, namely a reduction of the dielectric strength of about 71%, and an increase in secondary relaxation time of slightly less than one order of magnitude of the USG compared to the OG. The observed reduction of dielectric strength and increase of relaxation time in USG glasses was also reported for toluene, a much simpler molecule which exhibits a well resolved genuine JG β-relaxation with relaxation times in good agreement with the primitive relaxation times.17 In spite of the difference in the nature of the secondary relaxation process, the observed change in properties between OG and USG of etoricoxib is clearly analogous to that of toluene. It reinforces the interpretation of the observed secondary relaxation as a JG γ-process, since it preserves the intermolecular characteristics and properties of the JG β-process. As we mentioned earlier, the secondary relaxation time above Tg follows a stronger temperature dependence compared to the glassy state (Fig. 2B). Even though the extraction of information in this frequency range (partially out from the accessible window) is very sensitive to data analysis (see ESI†), a tentative linear extrapolation of the secondary relaxation time in the liquid state intersects that of the USG at around 306 K. The same behavior is observed in Fig. 2C for the intensity of the process, i.e. the variation of intensity with temperature is stronger in the liquid state, and reaches a nearly constant value when the system is vitrified. Again, a tentative linear extrapolation of the process intensity in the liquid state intersects that of the USG at around 308 K. Interestingly, those extrapolated temperature values are compatible with the value of enthalpic Tf′ obtained from the calorimetric curve (inset of Fig. 1A). In other words, the equilibrium state between liquid and USG measured through the secondary relaxation is consistent with the equilibrium state measured with calorimetry through the structural relaxation process. Furthermore, as we show in Fig. 3, the time needed for the system at 306 K to reach the secondary relaxation time of the USG is 109.75 s or 178 years, very similar to the structural relaxation time of the liquid at that temperature (τα (306 K) = 1010.6 s). These observations are analogous to those recently reported for the JG β-relaxation process in toluene.17
Noticeably, at Tg the secondary relaxation time of the OG is approximately equal to the relaxation time of the USG at Ton around 33 K higher in temperature (elucidated by the blue dashed line in Fig. 2B). Both Ton of the USG and the Tg of the OG can be defined as the temperature at which the structural α-relaxation time τα = 102 s, and critical for transformation from glass to liquid. We can then restate the previous observation by saying that the value of the secondary relaxation time τ at the temperature at which τα = 100 s is the same in USG and OG. The same observation can be made from the reported data of USG of toluene (shown in the ESI†). In that case, the increase of the isochronal JG β-relaxation temperature, ΔTβ = 6 K, is coincident with the enhancement of Ton in the USG. The choice of τα = 102 s to define Tg or Ton is arbitrary. On the other hand, the heating rate employed in the measurement of the glass determines Ton and the corresponding τα. However, according to a recent work, the enhancement of Ton between USG and OG of indomethacin and toluene is nearly independent of the heating rate26 (i.e. the distance between the black and red vertical dashed lines in Fig. 2B is independent of the heating rate employed to determine Ton). Therefore, and also taking into consideration of the very similar values of activation energy of the secondary relaxation in USG and OG, the invariance of τJG at Ton holds regardless of the arbitrary chosen τα(Ton) value. All these observations from the comparison between USG and OG are analogous to concurrent changes of the α- and the JG-β relaxation times at different pressures, where the change of Tg defined by τα(Tg) = 100 s is matched by the corresponding change in ΔTβ. This is illustrated by the data of DGEBA (diglycidyl ether of bisphenol-A)27 in ESI,† and more examples can be given.28–30 In fact, as we also show in Fig. 2B, the secondary relaxation time of the etoricoxib OG at 400 MPa and at Tg of the system at that pressure falls also onto the same blue line. All these observations draw a scenario in which the structural and secondary relaxations are strongly linked, not only from the point of view of the physical state of the system (as seen from the coincidence of the enthalpic Tf′ value and the Tf′ obtained from the secondary relaxation characteristics), but also from the point of view of its transformation from glass to liquid.
In Fig. 4 we plot the secondary relaxation time of USG and OG as a function of pressure at two different temperatures. We can clearly observe that the difference in relaxation time exhibited at ambient pressure (around 1 decade) is reduced as the pressure increases. At sufficiently high pressures, both systems exhibit a similar relaxation time. This result is very similar to the one reported in a recent work performed on indomethacin USG. There, Ton was measured as a function of the applied pressure, finding that the difference in Ton approached 0 as the pressure was increased to about 300 MPa.32 By means of a phenomenological model, the authors of ref. 32 claimed that the observed behavior could be explained by a convergence of density in both systems as pressure was increased. This explanation is compatible with the finding in this work. Moreover, if the secondary relaxation times of USG and OG are approaching each other at elevated pressures (as represented in Fig. 4 as well as on the high-pressure data plotted in Fig. 2B), and considering the mentioned invariance of τJG at Ton, as observed from Fig. 2B, then necessarily Ton must also approach each other as pressure is increased, suggesting again the correspondence between structural (responsible for the devitrification at Ton) and the secondary processes. Importantly, we notice from the inset in Fig. 4 that the observed variations in relaxation time of USG with pressure are reversible.
Even though the characteristics of the structural and secondary relaxations are linked together, the way that pressure affects those characteristics is not the same in USG and OG, as seen in Fig. 4. We give three plausible explanations for this issue. (i) The especial molecular arrangement of molecules in the USG may have an influence on the effect of pressure on the characteristics of the system. (ii) The distribution of relaxation times is not the same and, therefore, application of pressure affects differently the two systems. (iii) Density may not univocally determine the relaxation time, and therefore a different density of the system may yield a different evolution with pressure. According to the reported V(p,T) data for etoricoxib,21 the density of the OG at 122 MPa is around 2.1% higher than at ambient pressure. The expected change of density in USG is ∼2–3% from WAXS measurements. From these data, we see that changes in relaxation time induced by pressurization or by ultrastability are similar, since, according to Fig. 4, the relaxation times of USG at ambient pressure and OG at 122 MPa are equal. However, we have to be cautious with this result since, according to the reported V(T) data of etoricoxib at 10 MPa,21 a change in Tf′ of 18 K corresponds to a change in density of 0.7%, meaning that other factors apart from density are responsible for the observed increase in relaxation time of USG compared to OG. We note that the exact V(T) relation in vacuum (during the formation of the USG, p = 1 × 10−12 MPa) and at 10 MPa, and therefore Δρ corresponding to ΔTf′ = 18 K, may be very different. In any case, further experiments are required to fully understand the nature of USG. It is important to remark that, notwithstanding, the origin of the different behavior of USG and OG affects both the structural and the secondary process in the same manner, emphasizing again the strong link between both processes.
In summary, from the analysis of the relaxation data of the secondary JG γ-process persistent in the glassy state of USG and OG of etoricoxib we have arrived at several conclusions. Firstly, the JG process of USG, deep in the glassy state, appears to be less than one order of magnitude slower as well as less intense. This behavior is analogous to the one observed in the JG-β process of toluene glasses,17 and is attributed to the density increase of USGs resulting in slowing down of molecular rearrangements. This finding may have a strong impact in the application of USG, since secondary relaxations are responsible for many properties of glassy systems.1,33,34 Secondly, even though the observed secondary process in etoricoxib is not the unresolved JG β-relaxation, their density/pressure dependence and connection to the structural relaxation are analogous and hence it is another JG process. Likely, this JG γ-relaxation involves a substantial part of the entire molecule and is the precursor of the JG β-relaxation. Thirdly and most importantly, we have found strong evidences of a close link between the evolution in the structural and secondary relaxations as a function of thermodynamic conditions (temperature and pressure). Three different observations bring us to this conclusion. (i) At Ton of either USG or OG, the secondary relaxation time is invariant. (ii) The secondary relaxation determines an equilibrium state which is consistent with the equilibrium state measured through properties involving the structural relaxation, such as the calorimetric enthalpy or aging time. (iii) The secondary relaxation times of USG and OG seem to converge to the same value at elevated pressures, in analogy to the convergence of Ton(p) observed in USG and OG of indomethacin.32 These findings support the view that the secondary relaxation is an indispensable precursor of the structural one, and also reaffirms the importance of using the secondary relaxation of aged systems, or ideally the USG, to probe the properties of the structural relaxation, which is inaccessible by other means.
Footnote |
† Electronic supplementary information (ESI) available: Supporting data concerning data fitting procedure, isothermal transformation of USG, invariance of τβ in toluene, additional data on DGEBA at variable pressure and additional details on Fig. 1B. See DOI: 10.1039/c7cp06445d |
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