Pressure-induced amorphous-amorphous transition in pre-densified silica glass: an experimental exploration of the potential energy landscape | Scientific Reports

Scientific Reports volume 15, Article number: 6719 (2025) Cite this article

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Despite the difficulty of experimentally studying polyamorphic transitions in high-Tg glasses, it is well known that silica glass has two high-density phases: the cold-compressed and hot-compressed high-density amorphous phases (c-HDA and h-HDA). By means of vibrational spectroscopy techniques under pressure, we first evidence that the yield strength under hydrostatic pressure is identical for glasses of similar density, whatever the thermo-mechanical history, showing that the elastic limit of a silica glass depends solely of its density. Our results also reveal the changes in the energy landscape of amorphous silica under high pressure. Above a certain threshold pressure, the energy barriers between the different amorphous phases vanish and the glass is automatically driven toward the c-HDA phase, whatever the initial structure and the temperature of compression. Very high pressures can therefore erase all traces of a glass’s thermodynamic history.

Silica is the most widely studied network-forming oxide, both theoretically and experimentally, for its exceptional physical properties, which make it of major industrial interest, but also because it is the archetype of strong, fully polymerised glass, with an open network of SiO4 tetrahedra. Knowledge of its thermodynamic behaviour enables us to gain a deeper understanding of non-equilibrium systems1. Since the pioneer work of Bridgmann2, the high-pressure studies on silica glass have revealed a fascinating mechanical behaviour: First, in the elastic deformation regime, the glass compressibility passes through a maximum around 2 GPa3,4,5,6,7,8,9. Secondly, plastic deformation above 9 GPa leads to significant permanent densification after unloading10,11,12,13,14,15,16,17,18,19, of the order of 21%, a much higher value than for other silicates20,21,22,23. Finally, a gradual density-hardening phenomenon, meaning the shift of the elastic yield under pressure, was observed24,25,26,27,28. To characterize this mechanical aging, the parameter Pmax (i.e. the maximal pressure undergone by the glass during compression), directly linked to the density, was introduced12,24. However, density itself is not sufficient to characterize silica glass, because densification process assisted by heating, i.e. hot-compression, produces glasses with different structures at the medium range order from those produced at ambient temperature29,30,31,32,33,34,35,36,37,38,39,40,41,42,43, and therefore glasses with different properties. Indeed, at equivalent density, a hot-compressed glass is thermodynamically more stable than a cold-compressed one44,45,46. On the other hand, some other properties such as elastic moduli are comparable13. By analogy with amorphous ice47,48, the existence of these different states and the anomalies observed have been explained theoretically in the framework of amorphous-amorphous transitions, which assumes the existence of megabasins in the potential energy landscape (PEL), correlated to states of different structures and densities49,50,51,52,53,54. To date, the most complete description (deduced from experiments) of the PEL of silica proposes the existence of three megabasins, associated to the three following states: LDA, c-HDA and h-HDA, respectively for Low-Density-Amorphous, cold and hot High-Density-Amorphous45. To better understand the behaviour of densified silica under pressure, we analysed the room temperature high-pressure response of pre-densified silica glasses by hot compression, and compared it with the mechanical behaviour of cold-densified silica. The results show that the elastic yield depends solely on the initial density of the glass, and not on the thermodynamic way used for densification. Moreover, we show that above a threshold pressure, whatever the temperature reached during the densification, the glass recovered after pressure release has the structure of a cold-compressed silica. This property allows to better describe the evolution of the potential energy landscape of silica under pressure.

Pure silica glass (suprasil 300 from Heraeus, with low OH content, less than 1 ppm) was used as starting material. Silica cylinders (5.7 ± 0.1mm in height and 3.95 ± 0.05mm in diameter) were compressed in a Belt press up to a pressure Pmax, with Pyrophyllite as pressure transmitting medium, then kept at a high temperature Tmax during 600s. The samples were then cooled by turning off the heat supply, and the pressure slowly released to atmospheric pressure.

The density of Belt densified silica samples was measured using the flotation method based on Archimede’s principle. Two different pressure and temperature conditions were applied in order to obtain different densities. The experimental conditions and density measurements are summarized in Table 1. Hereafter, the two densified samples will be named SiO2_Belt_10 and SiO2_Belt_16, with 10 and 16 corresponding approximately to the densification ratio compared to pristine silica (in %) of each sample respectively.

In order to study the mechanical behaviour of these hot-compressed silica glasses under hydrostatic pressure at room temperature, high-pressure cold-compression experiments were carried out in a Chervin-type diamond anvil cell (DAC). Pre-densified silica glass splinter with a typical size of 30 μm and ruby chips were placed in the metal gasket hole (200 μm in diameter) filled with 4:1 methanol-ethanol mixture as the pressure-transmitting medium. Samples were loaded at room temperature at different maximum pressures Pmax, then unloaded. Spectroscopic experiments were carried out ex situ on the recovered samples. The maximal pressures reached by the two samples are summarized in Table 2.

The mechanical behaviour of the pre-densified SiO2-Belt-d16 sample as a function of pressure has been also investigated in situ using the same DAC during loading/unloading cycle up to 22 GPa at room temperature, by means of Raman and Brillouin spectroscopy.

Raman measurements were recorded in a backscattering configuration using a 50× objective, without polarization, using a Horiba Jobin Yvon LabRAM HR micro-Raman spectrometer, and a Nd:YAG 532 nm laser wavelength excitation source. The elastic part of the scattered light was rejected by a notch filter, and the photons energy dispersion was achieved using a 600 lines/mm diffraction grating. Raman spectra were recorded by a CCD camera between 250 cm−1 and 1250 cm−1.

The Brillouin scattering signal was recorded using a Sandercock tandem Fabry Perot interferometer coupled with a microscope in back-scattering geometry. The excitation source used was a laser emitting at 532 nm.

Some relevant Raman spectra of the two pre-densified samples that underwent a loading/unloading cycle in DAC are plotted Fig. 1. The different maximal pressures reached are shown in this figure. The recorded spectra are normalized to the 800 cm−1 band, whose maximum intensity does not vary with densification, as has been demonstrated on densified silica glasses in multianvil high-pressure devices55.

Raman spectra of the two pre-densified samples recorded at atmospheric pressure after loading/unloading cycles performed at room temperature up to several maximal pressures Pmax. These spectra reveal the existence of two threshold pressures: an elastic limit and a saturation pressure. The Raman spectra recorded for Pmax above 20 GPa are similar and also correspond to the Raman spectrum of c-HDA silica glass12.

The Fig. 1a displays the Raman spectra recorded at Patmo after compression of the SiO2_Belt_d10 glass at 13.6 GPa, 14.8 GPa, 16.3 GPa and 24.6 GPa. The black spectra corresponds to the Raman spectra recorded at the outlet of the Belt press, i.e. the hot-compressed samples before the cold compression/decompression cycle. Typical features of h-HDA silica glasses can be found in these spectra, in particular a very low intensity of the D2 band located at 615 cm−129,30,31. The black Raman spectrum and the spectrum of the sample after a pressure cycle up to 13.6 GPa are similar, showing that the glass undergoes an elastic deformation up to 13.6 GPa. Consequently, the elastic yield of the SiO2_Belt_d10 glass is greater than 13.6 GPa. For Pmax = 14.8 GPa, the Raman spectrum shows some modifications compared with the pristine spectrum. The main band is slightly shifted toward higher frequencies and merges with the D1 band, initially located around 500 cm−1, implying that the D1 band is no longer distinguishable. These changes, albeit slight, indicate that the elastic limit has been exceeded. The Raman spectrum recorded after a pressure cycle up to 16.3 GPa shows strong disparities with previous spectra. The main band have shifted sharply to higher frequencies. Moreover, the shape of the main band, and more precisely its asymmetry, seems to indicate the growth of the D1 band located around 500 cm−1. The growth of the D2 band at 600 cm−1 and the broadening of the 800 cm−1 band are striking, and the high-frequency band initially located around 1050 cm−1 widens and moves towards lower frequencies, towards 1000 cm−1. Plastic deformation is therefore progressive, and its magnitude depends on the maximal pressure reached. However, the comparison of the two spectra at 16.3 GPa and 24.6 GPa, which are fairly close to each other, shows that plastic deformation saturates above a certain pressure threshold. In summary, the pre-densified SiO2_Belt_d10 glass exhibits two pressures thresholds during hydrostatic compression: an elastic limit around 14 GPa, and a saturation pressure around 20 GPa.

Figure 1b shows the same type of behaviour for the second pre-densified sample, SiO2_Belt_d16. The Raman spectrum of the pristine sample is different from the previous one, as the pre-densification conditions and therefore the densification ratio and structure are different. The main difference is the width of the main band, which is smaller for the higher-density sample. The spectrum does not change for a pressure Pmax below 16.7 GPa, but does change for a pressure cycle at Pmax between 16.7 GPa and 17.4 GPa, the range in which the elastic limit lies. The similarity between the two spectra at Pmax above 20 GPa again indicates the existence of a saturation pressure. Furthermore, for both samples, once saturation pressure is exceeded, the glasses are structurally identical, as shown by the comparison of the pink spectra Fig. 1.

In order to determine the elastic limit of the two pre-densified silica samples more precisely, we have plotted the Raman shift of the main band maximal intensity as a function of the maximum pressure reached in Fig. 2. We chose the main band because it is the most sensitive to plastic deformation24.

Raman shift of the maximum of the main band after unloading as a function of maximal pressure reached during loading/unloading cycles in DAC for the two pre-densified samples. The data are fitted by a sigmoidal curve (red solid line), and the elastic limits of the two samples are determined by the intersection between the tangent of the sigmoid (blue dotted line) at the inflection point and the asymptote at low frequency (green dotted line). The elastic limits obtained are 14.4 GPa and 16.5 GPa for SiO2_Belt_d10 and SiO2_Belt_d16 respectively.

Figure 2 shows that the main band shifts to higher frequencies with Pmax, as discussed above. For the SiO2_Belt_d10 sample, the main band maximum is initially located at 470 cm−1. The band shifts from 470 cm−1 to 520 cm−1 in the pressure interval between 13 and 18 GPa. The main band of sample SiO2_Belt_d16 shifts from 480 cm−1 up to 520 cm−1 in the pressure interval between 17 and 22 GPa.

It should be noted that the experimental data show a significant dispersion, due to several parameters: in addition to measurement uncertainties on the position of the Raman shift and the position of the ruby luminescence to deduce the pressure, the pressure is no longer perfectly homogeneous when the alcohol mixture solidifies above 10 GPa56. Therefore, for the same load, if several samples are placed in the DAC (or if the sample breaks during the load), the spatial dispersion of the samples implies a dispersion of the pressure undergone by each sample. This is what happened when the SiO2_Belt_d16 sample was loaded at 19.4 GPa. The sample was in four pieces after unloading, each with a different Raman spectrum. Despite this, thanks to the quantity of data, we were able to evaluate the elastic limit of the two samples. For that, we first fit the data with a sigmoidal curve, as is done in the literature11,12. However, as this function is monotonic and increasing, it is not sufficient on its own to determine the yield point. To estimate this threshold, we take the point of intersection between the low-frequency asymptote and the tangent at the inflection point of the sigmoid. The elastic limits obtained are 14.4 GPa and 16.5 GPa for SiO2_Belt_d10 and SiO2_Belt_d16 respectively. Using the same method on data from a previous Raman study12, the elastic limit of non-densified silica is evaluated at 10.2 GPa, a value consistent with the literature1,10,11,12,13.

To our knowledge, there are no data in the literature concerning the elastic limit of hot-compressed silica glass. However, the values obtained can be compared with previous data concerning cold-compressed silica glasses. It has been demonstrated by multiple loading/unloading cycles in the plastic domain, that the elastic limit of a cold-compressed silica glass, and more generally of silicate glasses, is equal to the maximum pressure reached during loading22,24,25. Since the maximum pressure reached is directly related to the density of the recovered glass, the elastic limit of a cold-compressed silica glass is determined by its density. The evolution of this pressure threshold as a function of density is well-established11,12. With the new data displayed in the present study, it is now possible to compare the elastic yield of cold-compressed and hot-compressed silica glasses of similar densities.

We have shown Fig. 2 that the sample densified in Belt press, with a densification ratio of 9.5% after decompression, has an elastic yield of 14.4 + 1.0 GPa. According to the literature, a cold-compressed silica glass with the same densification ratio has an elastic yield of 14.0 GPa11,12. Similarly, the elastic limit of a 15.5% cold-densified silica glass is around 16.2 GPa, a value comparable to that obtained for the SiO2_Belt_d16 sample (16.5 + 1.0 GPa)11,12. Taking into account experimental uncertainties, it therefore appears that the elastic limit of silica glass does not depend on the thermodynamic path followed during densification, but only on its resulting density.

The only published data on room temperature compression of hot-densified silica glass come from Guerette et al. 201531. In this paper, the authors demonstrate the higher mechanical stability of hot-densified glasses (T = 1100°C and pressure up to 8 GPa). Indeed, they show by Brillouin spectroscopy complete reversibility of the transformation under pressure at room temperature, for initial densification ratio between 17 and 25%. For example, their sample densified to 17% (p = 4GPa and T = 1100°C), then compressed up to 15 GPa at room temperature, does not undergo plastic deformation. Our results confirmed that the elastic yield of hot-compressed silica is not the same as pristine silica one (10 GPa), but is shifted towards higher values. Moreover, if the elastic yield depends only on glass density, as we have shown previously, the elastic yield of this 17% densified silica should be of the order of 17 GPa11,12. It is therefore not surprising that a loading/unloading cycle up to p = 15 GPa remains reversible. For the sample with density above 20%, the elastic limit is probably much higher than 20 GPa, and reversible behaviour under pressure is observed by Guerette et al. at least up to 25 GPa. Unfortunately, no data exists for such hot-densified samples above this pressure.

Strikingly, the two Raman spectra recorded above the threshold pressure are identical, and similar to that of a fully densified c-HDA silica. To take this study a step further, we probed the evolution of the SiO2_Belt_d16 sample during the compression/decompression cycle, using Raman and Brillouin spectroscopy, to compare its behaviour with the high-pressure response of a non-densified silica. We note that Brillouin and Raman data on the cold compression of pristine silica glass already exist in the literature26. The evolution of the Raman main band shift and the Brillouin longitudinal frequency shift over a pressure cycle up to Pmax = 22 GPa are displayed Fig. 3a,b respectively. The evolution of non-densified and pre-densified silica glass during compression is very different. However, at the end of the compression, the curves merge, and during unloading, the evolutions are similar. Thus, this experiment confirms that the silica glass retrieved from a very high-pressure compression at room temperature of a h-HDA phase is the same glass as silica glass recovered after cold compression of a pristine silica glass, i.e. c-HDA. In other words, high-pressure is capable of erasing the glass’s thermomechanical history. This is due to the gradual disappearance of the energy barriers between the various metastable states that reflect this thermodynamic history.

(a) Raman shift of the main band maximum of the pre-densified SiO2-Belt-d16 sample as a function of pressure during loading up to 22 GPa (blue circles) and unloading (orange circles) at room temperature. The results are compared with previous room temperature measurements from C. Sonneville et al.26 of pristine (non-densified) silica glass during loading (black squares) and unloading (red circles). (b) Brillouin longitudinal frequency shift of the pre-densified SiO2-Belt-d16 sample as a function of pressure during loading/unloading up to 22 GPa, compared with results from Sonneville of pristine silica. The colour code used is the same for (b) and (a). The red dashed lines indicate the identical behaviour of pre-densified silica and pristine silica glasses once the pressure threshold (above 20 GPa) has been exceeded.

Although the aim of this study is not to investigate in depth the structural changes during compression of pre-densified silica glass, which would require numerical simulations, we can, based on our measurements and data from literature, give some indications. At the short-range order, it is well known that the tetrahedral coordination of silicon atoms is fully restored at atmospheric pressure. Although our experiments do not allow us to demonstrate this, it has been demonstrated by a multitude of experimental studies and simulations19,43,57. Thereby, coordination change is not directly responsible for residual densification after cold or hot-compression. On the other hand, the transient states in which the five- and sixfold coordination of silicon appears can explain the structural reorganization at the medium-range order58. Concerning the medium range order, which is characterize by the rings distribution in silica, there is still no consensus on the structural rearrangements leading to permanent densification. For cold compression, most studies show an evolution of the distribution towards smaller cycles12,28. However, structural differences have been observed between hot and cold compression, with hot compression appearing less favourable to the formation of small cycles29,30,31. Finally, it should be noted that the latest studies on the subject seem to show that for both types of densification (cold and hot compression), ring distribution is not affected, and the residual densification is due solely to rings compaction33,34. From the Raman spectra displayed Fig. 1, the strong increase in the D2 band upon plastic deformation of the previously densified glass at high temperature seems to indicate a significant change of the medium range order through an increase in the number of small rings. We assume that this transition is induced by the transient 5-coordination of silicon, which should appear at the elastic limit pressure of a pre-densified silica, i.e. at a higher pressure than that of a non-densified silica glass. Clearly, numerical simulations on pre-densified glass under cold compression are needed to confirm this assumption.

The new data obtained in this study enable us to draw the evolution of the Potential Energy Landscape of silica glass as a function of pressure. A schematic representation of this evolution, based on the state of the art and the results obtained in our present study is displayed Fig. 4. We will use it as a basis for the following discussion. At atmospheric pressure, the LDA phase have a lower energy than the c-HDA and h-HDA phases. Indeed, it is well known that each HDA phase relaxes toward the LDA phase when it is heated at atmospheric pressure44,45,46. Furthermore, we can note that the h-HDA phase have higher energy barriers than the c-HDA, as evidenced by the fact that the thermal energy required to relax the h-HDA phase is much higher than that required to relax the c-HDA phase45.

Schematic representation of the evolution of the Potential Energy Landscape of silica under pressure, as a function of single simplified system coordinate. At atmospheric pressure, LDA is the phase of lowest energy, and h-HDA has higher energy barriers than c-HDA. At higher pressure, between atmospheric pressure and the elastic limit, the h-HDA is the lowest-energy phase and can therefore be reached by heating. Above the elastic limit, LDA local minimum gradually disappears, and LDA relaxes toward the c-HDA phase at room temperature; h-HDA can be reached with thermal energy. At very high pressure, beyond the threshold pressure around 20 GPa, only the minimum associated to the c-HDA phase persists. So, even if compression is carried out at high temperature, the c-HDA phase will be recovered after decompression if decompression is carried out at ambient temperature.

Let us now analyse the influence of pressure on the Energy Landscape. At moderate pressure, between 2 and 10 GPa, if silica glass is heated and cooled down before the pressure is released, h-HDA is obtained29,30,31. The position of local minima is therefore strongly influenced by pressure, and h-HDA phase has a lower energy than LDA at these pressures. However, the energy barriers between these two phases remain significant. They decrease further with pressure, as the higher the pressure, the less heating is required to reach the c-HDA phase.

Without heating and at pressures below the elastic limit Pelastic, the glass stays in its LDA phase24,25. The barrier between LDA and c-HDA reduces with increasing pressure, but still exists below Pelastic. Above this pressure, the LDA phase begins to relax toward the c-HDA, meaning that the local c-HDA minimum is lower, and the barrier is low enough to be crossed at room temperature12,24. It is likely that the LDA local minimum disappears progressively with pressure. Furthermore, our experiment shows that for any h-HDA samples compressed at room temperature, there is a pressure threshold that causes the glass to switch to the c-HDA phase. This seems to mean that a single minimum persists at very high pressure, corresponding to the c-HDA phase.

This interpretation is consistent with recent in situ Brillouin HP-HT data37. In this article, silica glass is compressed at pressure above 50 GPa at three temperatures: room temperature, 750K and 1000K. Once the maximal pressure has been reached, each sample is cooled down to room temperature before decompression. It can be seen that for the three samples, decompression takes place in exactly the same way: no dispersion is observed on the values of longitudinal and shear velocities of the three glasses during unloading. This is because, at very high pressure, the structure of h-HDA no longer has a local energy minimum, and only c-HDA still has one. So, whatever the compression temperature, all three glasses are in the same thermodynamic state. This interpretation also explain the X-ray experiments of Inamura et al.40. In this in situ HP-HT study, the authors tracked the FSDP position at several pressure as a function of the temperature from Tamb to about 900°C. They have revealed that for intermediate pressures, from 3.7 GPa to 11.9 GPa, temperature induced relaxation toward higher density glasses. This relaxation is only possible because there are at least two metastable states in the PEL at those pressures. However, at 19.2 GPa, no shift of the FSDP was observed, which confirm the presence of one single minimum in the PEL at very high pressure. At least, the results obtained by Liang et al.41, using Molecular Dynamics simulations, can also be considered in this context. In this study, the structure factor of cold and hot-compressed silica glasses is calculated and compared at different pressures. The authors show that at each pressure, the short-range order is identical, but at the medium-range order, structural differences between the two glasses appear between atmospheric pressure and a pressure threshold. At very high pressure (above 20 GPa), the structure factors are very similar.

To conclude, this study has enabled us to gain a better understanding of the PEL of silica glass, and in particular its behaviour under pressure. We have also demonstrate that the elastic limit of silica glass depends only on its density, whatever the type of compression, i.e. with or without heating. However, there are other densification methods such as electrons or laser irradiation59,60. Future research will be carried out to determine whether the law obtained on the evolution of elastic limit applies to all types of densified glass, whatever the way of densification, or whether this law is restricted to mechanical densification.

The datasets used during this study are available from the corresponding author on reasonable request.

Du, T., Sorensen, S., To, T. & Smedskjaer, M. Oxide glasses under pressure: Recent insights from experiments and simulations. J. Appl. Phys. 131, 170901 (2022).

Article ADS CAS Google Scholar

Bridgman, P. W. & Simon, I. Effects of very high pressures on glass. J. Appl. Phys. 24, 405–413 (1953).

Article ADS CAS MATH Google Scholar

Grimsditch, M. Polymorphism in amorphous SiO2. Phys. Rev. Lett. 52, 2379–2381 (1984).

Article ADS CAS MATH Google Scholar

Zha, C. S., Hemley, R. J., Mao, H. K., Duffy, T. S. & Meade, C. Acoustic velocities and refractive-index of SiO2 glass to 57.5-GPa by Brillouin-scattering. Phys. Rev. B 50, 13105–13112 (1994).

Article ADS CAS Google Scholar

Sen, S., Andrus, R. L., Baker, D. E. & Murtagh, M. T. Observation of an anomalous density minimum in vitreous silica. Phys. Rev. Lett. 93, 125902 (2004).

Article ADS PubMed Google Scholar

Huang, L. & Kieffer, J. Amorphous-amorphous transitions in silica glass. I. Reversible transitions and thermomechanical anomalies. Phys. Rev. B 69, 224203 (2004).

Article ADS MATH Google Scholar

Deschamps, T., Martinet, C., De Ligny, D. & Champagnon, B. Elastic anomalous behavior of silica glass under high-pressure: In-situ Raman study. J. Non-Cryst. Solids 355, 1095–1098 (2009).

Article ADS CAS Google Scholar

Clark, A. N., Lesher, C. E., Jacobsen, S. D. & Sen, S. Mechanisms of anomalous compressibility of vitreous silica. Phys. Rev. B 90, 174110 (2014).

Article ADS Google Scholar

Mantisi, B., Tanguy, A., Kermouche, G. & Barthel, E. Atomistic response of a model silica glass under shear and pressure. Eur. Phys. J. B 85, 304 (2012).

Article ADS Google Scholar

Huang, L. & Kieffer, J. Amorphous-amorphous transitions in silica glass. II. Irreversible transitions and densification limit. Phys. Rev. B 69, 224204 (2004).

Article ADS MATH Google Scholar

Rouxel, T., Ji, H., Hammouda, T. & Moréac, A. Poisson’s ratio and the densification of glass under high pressure. Phys. Rev. Lett. 100, 225501 (2008).

Article ADS CAS PubMed MATH Google Scholar

Deschamps, T. et al. Permanent densification of compressed silica glass: a Raman-density calibration curve. J. Phys. Condens. Matter 25, 025402 (2013).

Article ADS CAS PubMed MATH Google Scholar

Deschamps, T., Margueritat, J., Martinet, C., Mermet, A. & Champagnon, B. Elastic moduli of permanently densified silica glasses. Sci. Rep. 4, 7193 (2014).

Article ADS CAS PubMed PubMed Central Google Scholar

Hemley, R., Mao, H., Bell, P. & Mysen, B. Raman-spectroscopy of SiO2 glass at high-pressure. Phys. Rev. Lett. 57, 747–750 (1986).

Article ADS CAS PubMed MATH Google Scholar

Meade, C., Hemley, R. J. & Mao, H. K. High-pressure x-ray diffraction of SiO2 glass. Phys. Rev. Lett. 69, 1387–1390 (1992).

Article ADS CAS PubMed Google Scholar

Mukherjee, G. D., Vaidya, S. N. & Sugandhi, V. Direct observation of amorphous to amorphous apparently first-order phase transition in fused quartz. Phys. Rev. Lett. 87, 195501 (2001).

Article ADS CAS PubMed Google Scholar

Tsiok, O. B., Brazhkin, V. V., Lyapin, A. G. & Khvostantsev, L. G. Logarithmic kinetics of the amorphous–amorphous transformations in SiO2 and GeO2 glasses under high-pressure. Phys. Rev. Lett. 80, 999–1002 (1998).

Article ADS CAS Google Scholar

Rouxel, T., Ji, H., Guin, J. P., Augereau, F. & Rufflé, B. Indentation deformation mechanism in glass: Densification versus shear flow. J. Appl. Phys. 107, 094903 (2010).

Article ADS Google Scholar

Liang, Y., Miranda, C. R. & Scandolo, S. Mechanical strength and coordination defects in compressed silica glass: Molecular dynamics simulations. Phys. Rev B 75, 024205 (2007).

Article ADS Google Scholar

Lee, S. K. et al. Degree of permanent densification in oxide glasses upon extreme compression up to 24 GPa at room temperature. J. Phys. Chem. Lett. 11, 2917–2924 (2020).

Article CAS PubMed Google Scholar

Deschamps, T., Martinet, C., Bruneel, J. L. & Champagnon, B. Soda-lime silicate glass under hydrostatic pressure and indentation: a micro-Raman study. J. Phys. Condens. Matter 23, 035402 (2011).

Article ADS CAS PubMed Google Scholar

Deschamps, T., Martinet, C., Champagnon, B., Molnár, G. & Barthel, E. Memory effect in the plasticity of a silicate glass densified at room temperature. Phys. Rev. B 105, 224206 (2022).

Article ADS CAS Google Scholar

Kilymis, D. A., Delaye, J. M. & Ispas, S. Behavior of sodium borosilicate glasses under compression using molecular dynamics. J. Chem. Phys. 143, 094503 (2015).

Article ADS CAS PubMed Google Scholar

Vandembroucq, D. et al. Density hardening plasticity and mechanical ageing of silica glass under pressure: a Raman spectroscopic study. J. Phys. Condens. Matter 20, 485221 (2008).

Article MATH Google Scholar

Champagnon, B. et al. High pressure elastic and plastic deformations of silica: In situ diamond anvil cell Raman experiments. J. Non-Cryst. Solids 354, 569–573 (2008).

Article ADS CAS Google Scholar

Sonneville, C. et al. Progressive transformations of silica glass upon densification. J. Chem. Phys. 137, 124505 (2012).

Article ADS CAS PubMed MATH Google Scholar

Trease, N. M., Clark, T. M., Grandinetti, P. J., Stebbins, J. F. & Sen, S. Bond length-bond angle correlation in densified silica—Results from 17O NMR spectroscopy. J. Chem. Phys. 146, 184505 (2017).

Article ADS Google Scholar

Koziatek, P., Barrat, J.-L. & Rodney, D. Short- and medium-range orders in as-quenched and deformed SiO2 glasses: An atomistic study. J. Non-cryst. Solids 414, 7 (2015).

Article ADS CAS Google Scholar

Poe, B. T., Romano, C. & Henderson, G. Raman and XANES spectroscopy of permanently densified vitreous silica. J. Non-Cryst. Solids 341, 162–169 (2004).

Article ADS CAS Google Scholar

Martinet, C. et al. Permanent densified SiO2 glasses: a structural approach. J. Phys. Condens. Matter 27, 325401 (2015).

Article CAS PubMed MATH Google Scholar

Guerette, M. et al. Structure and properties of silica glass densified in cold compression and hot compression. Sci. Rep. 5, 15343 (2015).

Article ADS CAS PubMed PubMed Central Google Scholar

Kapoor, S., Wondraczek, L. & Smedskjaer, M. M. Pressure-induced densification of oxide glasses at the glass transition. Front. Mater. 4, 1–20 (2017).

Article ADS Google Scholar

Onodera, Y. et al. Structure and properties of densified silica glass: characterizing the order within disorder. NPG Asia Mater. 12, 85 (2020).

Article ADS CAS MATH Google Scholar

Salmon, P. S. et al. Ring compaction as a mechanism of densification in amorphous silica. Phys. Rev. B 107, 144203 (2023).

Article ADS CAS MATH Google Scholar

Kobayashi, K. et al. Machine learning molecular dynamics reveals the structural origin of the first sharp diffraction peak in high-density silica glasses. Sci. Rep. 13, 18721 (2023).

Article ADS CAS PubMed PubMed Central Google Scholar

Inamura, Y. et al. Intermediate range structure and low-energy dynamics of densified vitreous silica. J. Non-Cryst. Solids 293–295, 389–393 (2001).

Article ADS MATH Google Scholar

Sun, N., Mao, Z., Zhang, X., Tkachev, S. N. & Lin, J. F. Hot dense silica glass with ultrahigh elastic moduli. Sci. Rep. 12, 13946 (2022).

Article ADS CAS PubMed PubMed Central MATH Google Scholar

Yuan, F. & Huang, L. Brittle to ductile transition in densified silica glass. Sci. Rep. 4, 5035 (2014).

Article ADS CAS PubMed PubMed Central MATH Google Scholar

Zanatta, M. et al. Structural evolution and medium range order in permanently densified vitreous SiO2. Phys. Rev. Lett. 112, 045501 (2014).

Article ADS CAS PubMed MATH Google Scholar

Inamura, Y., Katayama, Y., Utsumi, W. & Funakoshi, K. Transformations in the intermediate-range structure of SiO2 glass under high pressure and temperature. Phys. Rev. Lett. 93, 015501 (2004).

Article ADS MATH Google Scholar

Liang, Y., Miranda, C. R. & Scandolo, S. Temperature-induced densification of compressed SiO2 glass: A molecular dynamics study. High Press. Res. 28, 35–44 (2008).

Article ADS CAS MATH Google Scholar

Kono, Y. et al. Experimental evidence of tetrahedral symmetry breaking in SiO2 glass under pressure. Nat. Commun. 13, 2292 (2022).

Article ADS CAS PubMed PubMed Central MATH Google Scholar

Lin, J. et al. Electronic bounding transition in compressed SiO2 glass. Phys. Rev. B 75, 012201 (2007).

Article ADS MATH Google Scholar

Cornet, A., Martinez, V., de Ligny, D., Champagnon, B. & Martinet, C. Relaxation processes of densified silica glass. J. Chem. Phys. 146, 094504 (2017).

Article ADS Google Scholar

Guerette, M., Ackerson, M. R., Tomas, J., Watson, E. B. & Huang, L. Thermally induced amorphous to amorphous transition in hot-compressed silica glass. J. Chem. Phys. 148, 194501 (2018).

Article ADS PubMed Google Scholar

Cornet, A., Martinet, C., Martinez, V. & de Ligny, D. Evidence of polyamorphic transitions during densified SiO2 glass annealing. J. Chem. Phys. 151, 164502 (2019).

Article ADS PubMed Google Scholar

Mishima, O., Calvert, L. D. & Whalley, E. An apparently first-order transition between two amorphous phases of ice induced by pressure. Nature 314, 76–78 (1985).

Article ADS CAS Google Scholar

Poole, P. H., Sciortino, F., Essmann, U. & Stanley, H. E. Phase behaviour of metastable water. Nature 360, 324–328 (1992).

Article ADS CAS MATH Google Scholar

Debenedetti, P. G. & Stillinger, F. H. Supercooled liquids and the glass transition. Nature 410, 259–267 (2001).

Article ADS CAS PubMed MATH Google Scholar

Saika-Voivod, I., Poole, P. H. & Sciortino, F. Fragile-to-strong transition and polyamorphism in the energy landscape of liquid silica. Nature 412, 514–517 (2001).

Article ADS CAS PubMed Google Scholar

Angell, C. A., Ngai, K. L., McKenna, G. B., McMillan, P. F. & Martin, S. W. Relaxation in glass forming liquids and amorphous solids. J. Appl. Phys. 88, 3113–3157 (2000).

Article ADS CAS Google Scholar

McMillan, P. F., Wilson, M., Daisenberger, D. & Machon, D. A density-driven phase transition between semiconducting and metallic polyamorphs of silicon. Nature mater. 4, 680–684 (2005).

Article ADS CAS Google Scholar

Sastry, S. & Austen Angell, C. Liquid–liquid phase transition in supercooled silicon. Nat. Mater. 2, 739–743 (2003).

Article ADS CAS PubMed MATH Google Scholar

Sheng, H. W. et al. Polyamorphism in a metallic glass. Nat. Mater. 6, 192–197 (2007).

Article ADS CAS PubMed MATH Google Scholar

Burgin, J. et al. Vibrational modes and local order in permanently densified silica glasses: Femtosecond and Raman spectroscopy study. Phys. Rev. B 78, 184203 (2008).

Article ADS Google Scholar

Klotz, S., Chervin, J. C., Munsch, P. & Le Marchand, G. Hydrostatic limits of 11 pressure transmitting media. J. Phys. D: Appl. Phys. 42, 075413 (2009).

Article ADS Google Scholar

Ryuo, E., Wakabayashi, D., Koura, A. & Shimojo, F. Ab initio simulation of permanent densification in silica glass. Phys. Rev. B 96, 054206 (2017).

Article ADS Google Scholar

Zeidler, A. et al. High-pressure transformation of SiO 2 glass from a tetrahedral to an octahedral network: A joint approach using neutron diffraction and molecular dynamics. Phys. Rev. Lett. 113, 135501 (2014).

Article ADS PubMed MATH Google Scholar

Ollier, N. et al. Relaxation study of pre-densified silica glasses under 2.5 MeV electron irradiation. Sci. Rep. 9, 1227 (2019).

Article ADS PubMed PubMed Central MATH Google Scholar

Shcheblanov, N. S., Povarnitsyn, M. E., Mishchik, K. N. & Tanguy, A. Raman spectroscopy of femtosecond multipulse irradiation of vitreous silica: Experiment and simulation. Phys. Rev. B 97, 054106 (2018).

Article ADS CAS Google Scholar

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Institut Lumière Matière UMR CNRS 5306, Université Claude Bernard Lyon 1, CNRS, 69622, Villeurbanne, France

M. Courtois, A. Berthelot, S. Le Floch, C. Martinet & T. Deschamps

Institut Néel, Université Grenoble Alpes and Centre National de la Recherche Scientifique, 25 rue des Martyrs, BP 166, 38042, Grenoble Cedex 9, France

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TD designed the research. MC, AB, AC, SLF, CM and TD performed the experiments. MC and TD processed and analysed the data. TD wrote the manuscript.

Correspondence to T. Deschamps.

The authors declare no competing interests.

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Courtois, M., Berthelot, A., Cornet, A. et al. Pressure-induced amorphous-amorphous transition in pre-densified silica glass: an experimental exploration of the potential energy landscape. Sci Rep 15, 6719 (2025). https://doi.org/10.1038/s41598-025-89802-7

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Received: 07 January 2025

Accepted: 07 February 2025

Published: 25 February 2025

DOI: https://doi.org/10.1038/s41598-025-89802-7

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