Article

pubs.acs.org/JPCB

Dissolution Kinetics of Hot Compressed Oxide Glasses

Nerea Mascaraque,† Mathieu Bauchy,‡ José Luis G. Fierro,§ Sylwester J. Rzoska,∥ Michal Bockowski,∥
and Morten M. Smedskjaer*,†
†
Department of Chemistry and Bioscience, Aalborg University, 9220 Aalborg, Denmark
‡
Department of Civil and Environmental Engineering, University of California, Los Angeles, California 90095, United States
§
Instituto de Catálisis y Petroleoquímica (CSIC), Cantoblanco, 28049 Madrid, Spain
∥
Institute of High-Pressure Physics, Polish Academy of Sciences, 01-142 Warsaw, Poland
*
S Supporting Information

ABSTRACT: The chemical durability of oxide glasses is an important

property for a wide range of applications and can in some cases be tuned
through composition optimization. However, these possibilities are
relatively limited because around 3/5 of the atoms in most oxide glasses
are oxygens. An alternative approach involves post-treatment of the glass.
In this work, we focus on the effect of hot compression on dissolution
kinetics because it is known to improve, for example, elastic moduli and
hardness, whereas its effect on chemical durability is poorly understood.
Specifically, we study the bulk glass dissolution rate of phosphate,
silicophosphate, borophosphate, borosilicate, and aluminoborosilicate
glasses, which have been compressed at 0.5, 1.0, and 2.0 GPa at the
glass transition temperature (Tg). We perform weight loss and
supplementary modifier leaching measurements of bulk samples immersed
in acid (pH 2) and neutral (pH 7) solutions. Compression generally
improves the chemical durability as measured from weight loss, but the effect is highly composition- and pressure-dependent. As
such, we show that the dissolution mechanisms depend on the topological changes induced by permanent densification, which in
turn are a function of the changes in the number of nonbridging oxygens and the network cross-linking. We also demonstrate a
direct relationship between the chemical durability and the number of chemical topological constraints per atom (nc) acting
within the molecular network.

I. INTRODUCTION occurs at a significantly lower pressure, thus enabling

preparation of bulk samples.
Various approaches for tuning the dissolution rate of glasses are
The effect of compression on chemical durability remains
currently being investigated, such as intrinsic composition
relatively poorly understood. Zhang et al. showed that the
optimization involving growth of silver particles,1 rare-earth
densification of silicate and borate glasses at a pressure up to 5
introduction,2 and substitution of elements.3−5 However, GPa at Tg improves the resistance to corrosion.19,20 We note
around 3/5 of the atoms in most oxide glasses are oxygens that densification can involve various mechanisms, which can
and the possibilities for property tuning are thus relatively alter the dissolution in different ways. (i) Densification is
limited. Many efforts are therefore also focusing on various associated with a lower amount of free volume within the
post-treatment methods, such as cold and hot solution atomic network, which is likely to slow down the migration of
treatment,6 fire polishing,7 gaseous-reagent treatment,8 coating hydration species through the glass. (ii) Densification can also
with polymers as grafting-from method,9 coating with metal,10 result in the appearance of some structural defects within the
and SO2 surface treatment.11 As an alternative route to enhance network, for example, Si−O−Si angular distortions. Such
or tune the corrosion rate, we here investigate hot isostatic distortions are likely to result in the formation of some internal
compression, which is a method that does not induce a stress, thereby rendering the network less stable and more
compositional modification of the glass and could also improve prone to dissolve. (iii) An increase in pressure can lead to the
other properties, such as elastic moduli and hardness.12,13 The formation of over-coordinated species (e.g., through the
permanent densification of oxide glasses can be achieved by conversion of 3-fold into 4-fold coordinated B atoms). The
cold compression at pressures above 8−10 GPa,14,15 but most resulting increase in the glass connectivity (or degree of
characterization of such densified samples would be prohibited
due to their typical small sample volumes. By increasing the Received: May 11, 2017
temperature during compression, for example, to the glass Revised: August 30, 2017
transition temperature (Tg),16−18 permanent densification Published: September 1, 2017

© 2017 American Chemical Society 9063 DOI: 10.1021/acs.jpcb.7b04535

J. Phys. Chem. B 2017, 121, 9063−9072
The Journal of Physical Chemistry B Article

polymerization) is likely to increase the resistance to compositions from a previous study,25 including phosphate,
dissolution. As such, the effect of the pressure on dissolution silicophosphate, borophosphate, borosilicate, and aluminobor-
kinetics is nontrivial and might result from a balance of several osilicate systems. The selected compositions were 36Na2O·
competing mechanisms. 64P 2 O 5 , 30Na 2 O·20SiO 2 ·50P 2 O 5 , 50CaO·5B 2 O 3 ·45P 2 O 5 ,
In this work, we study the dissolution behavior of phosphate- 15Na2O·10CaO·15B2O3·60SiO2, and 15Na2O·17Al2O3·5B2O3·
and silicate-based glasses subjected to permanent densification 63SiO2 (in mol %) and are referred to as P, SiP, BP, BSi, and
under pressures up to 2 GPa at Tg. When phosphate- or silicate- AlBSi, respectively (Table 1). The five glasses were prepared
based glasses come in contact with an aqueous solution, two
main processes occur individually or in combination:21,22 (i) Table 1. Nominal Compositions (in mol %), Hot
ion exchange involving diffusion between M(+, 2+) (e.g., Na+, Compression Treatment, and Calculated Number of
Ca2+) close to nonbridging oxygens (NBOs) and protonated Constraints Per Atom (nc) of the Investigated Oxide
species and (ii) hydrolysis involving dissolution of phosphate or Glassesa
silicate chains as a consequence of the breaking of P−O−P and
composition (in mol %) P (GPa) nc (−) reference
Si−O−P bonds. The densification of silicate and borate
glasses19,20 induces a decrease of the average bond angle and 36Na2O·64P2O5 P glass ambient 2.76 32
void volume, producing an improvement of chemical durability. 0.5 2.84 this work
However, water corrosion depends not only on the shortening 1.0 2.86 this work
of the bond length or the decrease of void volumes but also on 2.0 2.84 this work
the changes in the coordination number of the network-formers 30Na2O·20SiO2·50P2O5 SiP glass ambient 2.90 32
(e.g., P, Si, B, or Al) and the concentration of NBOs. For 0.5 2.96 this work
example, many dissolution studies21−23 have focused on the 1.0 2.98 this work
effect of the number of NBOs, that is, the degree of network 2.0 2.90 this work
connectivity, on the resistance to corrosion. In recent studies of 50CaO·5B2O3·45P2O5 BP glass ambient 3.01 33
oxide glasses,24,25 a direct relation has been demonstrated 0.5 3.06 this work
between the dissolution rate and the number of chemical 1.0 3.09 this work
topological constraints per atom (nc) acting within the 2.0 3.13 this work
molecular network. Topological constraint theory26−28 has 15Na2O·10CaO·15B2O3·60SiO2 BSi glass ambient 3.35 34
been used to establish the dependence of various glass 0.5 3.50 this work
properties on the balance between the number of atomic 1.0 3.53 this work
degrees of freedom and the number of interatomic chemical 2.0 3.54 this work
constraints. For a three-dimensional system, each atom has 15Na2O·17Al2O3·5B2O3·63SiO2 AlBSi ambient 3.63 35
glass 0.5 3.73 this work
three translational degrees of freedom, which are removed
through the presence of rigid bond constraints, that is, two- 1.0 3.76 this work
body bond stretching (BS) and three-body bond bending 2.0 3.92 this work
a
constraints. The values of nc of the as-prepared glasses are taken from refs32−35,
Here, we apply such a topological approach to understand whereas the calculation of nc for the densified glasses is explained in
the chemical durability of densified oxide glasses by studying the text.
the dissolution behavior in acidic and neutral solutions of
phosphate, silicophosphate, borophosphate, borosilicate, and using the melt-quenching method by mixing batches of the
aluminoborosilicate glasses previously compressed at 0.5, 1.0, following reagent-grade materials: Na2CO3 (99.999% Suprapur,
and 2.0 GPa at their respective Tg. The activation energies Merck), CaCO3 (Reag. Ph Eur, Merck), NH4H2PO4 (≥98%
needed to break a unit atomic constraint during dissolution are ACS Reagent, Sigma-Aldrich), v-B2O3 (B2O3 previously melted
calculated for the densified samples at pHs 2 and 7. We discuss at 850 °C using H3BO3 as raw material), SiO2 (Sigma-Aldrich,
these results based on structural characterization using X-ray purum p.a.), and Al2O3 (Sigma-Aldrich, ≥99%). The melt-
photoelectron spectroscopy (XPS) and supplementary meas- quenching procedure is described in detail elsewhere.25
urements of the concentration of leached calcium and sodium Samples of each oxide glass were cut to rectangular shape
modifier cations using atomic absorption spectroscopy (AAS). (approximately 0.7 × 0.6 × 0.3 cm3), and their faces were
We show a direct relationship between the pressure-induced polished using a 4000-grit SiC paper at the final step. These
changes in nc and the dissolution rates, suggesting that with hot samples were isostatically compressed at 0.5, 1.0, and 2.0 GPa
compression and the use of existing topological models, the at their respective glass-transition temperature in a nitrogen gas
design of oxide glasses with a specific chemical durability for a pressure reactor using a vertically positioned chamber for
determined pH could become possible. As such, the aim of the pressures of 0.5 and 1 GPa and horizontally positioned for a
present study is not to provide additional understanding of the pressure of 2.0 GPa. The samples were heated at a constant rate
details of the glass dissolution mechanism but rather to enable of 600 °C/h to their Tg values, kept under N2 pressure for 30
prediction of the overall practical glass dissolution rate as min, and subsequently quenched with a cooling rate of 60 °C/
calculated from the weight loss measurements. For most min and a decompression rate of 30 MPa/min at room
industrial applications of glass, weight loss experiments provide temperature. Additional details about this high-pressure setup
valuable data and mimic industrial application conditions more can be found in ref29.
accurately than controlled dissolution leaching tests. X-ray photoelectron spectra (XPS) of as-prepared and
densified powder samples were obtained with a VG Escalab
II. EXPERIMENTAL SECTION 200R spectrometer equipped with a hemispherical electron
To study the effect of compression on chemical durability in analyzer and a Mg Kα (hν = 1253.6 eV) X-ray source, powered
various oxide glass systems, we have selected five different at 100 W. The kinetic energies of photoelectrons were
9064 DOI: 10.1021/acs.jpcb.7b04535
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The Journal of Physical Chemistry B Article

measured using a hemispherical electron analyzer working in

the constant-pass energy mode (pass energy of 20 eV). The
background pressure in the analysis chamber was kept below 8
× 10−9 mbar during data acquisition. The XPS data signals were
taken in increments of 0.07 eV and with dwell times of 50 ms.
Binding energies were calibrated relative to the C 1s peak at
284.8 eV. High-resolution spectra envelopes were obtained by
curve fitting synthetic peak components using software XPS
peak. The raw data were used with no preliminary smoothing.
Symmetric Gaussian−Lorentzian functions were used to
approximate the line shapes of the fitting components. Atomic
ratios were computed from experimental intensity ratios and
normalized by atomic sensitivity factors.30
To evaluate the effect of the high-pressure treatment on the
network densification, we determined the density (ρ) and
Vickers hardness (HV) of the as-prepared and densified glasses.
Density was measured at room temperature using the
Archimedes method. The weight of each glass was measured
in ethanol using a balance measuring to ±0.1 mg and repeated
10 times in each glass to determine the standard deviation.
Hardness was determined using Vickers microindentation with
a Duramin 5 microindenter (Struers A/S) equipped with a
Vickers geometry diamond tip. Prior to indentation, the
samples were polished using water-free diamond suspensions
to avoid surface hydration. Each sample was indented at least
30 times in air at room temperature using a load of 0.49 N and
a dwell time of 15 s.
Prior to the measurements of durability, the densified
samples were cleaned with distilled water under ultrasonication
for 5 min and then with acetone under ultrasonication for 5
min and finally dried in an oven at 105 °C for 1 h. Afterward,
the weight and surface area were measured. Aqueous solutions
(50 mL) of 2 mM HCl and distilled water were used to obtain
pH values of 2 and 7, respectively. For each experiment, the
solid-to-liquid ratio was selected to be low enough to avoid any
saturation effect. The bulk dissolution rate of each glass was
determined by measuring the weight loss after immersion of the
bulk sample in acidic (pH 2) and neutral (pH 7) aqueous
solutions at room temperature as a function of time (t in hour)
and the pressure (P in GPa) used during the hot compression
treatment. The experiment was repeated twice for each glass
composition in each solution. The pH of the media was
measured as a function of dissolution time using a pH meter
(M220-X9541) and maintained constant throughout the
experiments by adding basic or acid solutions. Note that the
duration of the dissolution test was adjusted for each glass
(from 4 h to nearly 3 months) to achieve substantial values of Figure 1. Deconvolution of O 1s core-level spectra of as-prepared and
weight loss. In addition to studying the bulk dissolution rates of compressed SiP glasses. The dashed and solid lines represent the
the samples, the leaching of calcium and sodium ions was also experimental and fitted data, respectively.
investigated after the end of bulk dissolution testing, that is,
after the longest immersion time. The concentrations of Na+ The spectra of the four other glass series are shown in Figures
and Ca2+ (in ppm) were determined using atomic absorption S1−S4 in the Supporting Information. According to the model
spectrometry (AAnalyst 100, PerkinElmer). of Brückner,31 the O 1s spectra of phosphate-based glasses
(glasses SiP, P, and BP in Figures 1, S1, and S2, respectively)
III. RESULTS AND DISCUSSION should be deconvoluted in three Gaussian−Lorentzian mixed
III.I. X-ray Photoelectron Spectroscopy. To establish the components (Voigt profile) attributed to two nonbridging
impact of the number of nonbridging oxygens (NBOs) on oxygens, PO and M(+ or 2+)···−O−P, at 531.1 and 532.0 eV,
dissolution rates, we have used XPS to determine the number respectively, and bridging oxygens, P−O−P, B−O−P, and/or
of bridging oxygens (BOs) and NBOs from the deconvolution Si−O−Si, at 533.1 eV. For the silicate-based glasses (glasses BSi
of the O 1s core-level peak. Because of the large number of XPS and AlBSi in Figures S3 and S4, respectively, in the Supporting
spectra (as-prepared, 0.5, 1, and 2 GPa samples for the five Information), the O 1s peak is deconvoluted in two Gaussian−
compositions), we here show only the XPS spectra of the O 1s Lorentzian mixed components associated with NBOs (Si−O−)
peak for the as-prepared and compressed SiP glasses (Figure 1). at 530.4 eV and BO (Al−O−Si, B−O−Si, and/or Si−O−Si) at
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Table 2. Fractions of Bridging and Nonbridging Oxygens (BOs and NBOs) of the As-Prepared and Compressed Glassesa
deconvolution of O 1s XPS peak
as-prepared compressed at 0.5 GPa compressed at 1.0 GPa compressed at 2.0 GPa
ID BO (%) NBO (%) BO (%) NBO (%) BO (%) NBO (%) BO (%) NBO (%)
P 35.3 64.7 39.8 60.2 42.3 57.7 41.6 58.4
SiP 36.0 64.0 38.4 61.6 37.9 62.1 37.1 62.9
BP 28.4 71.6 29.9 70.1 29.2 70.8 28.5 71.5
BSi 92.4 7.6 87.4 12.6 86.9 13.1 89.0 11.0
AlBSi 94.5 5.5 96.5 3.5 96.1 3.9 98.3 1.7
a
The error is smaller than ±0.5%.

Figure 2. (a) Density (ρ in g cm−3) and (b) Vickers hardness (HV in GPa) of the five glass compositions as a function of the applied pressure (P in
GPa) at the glass-transition temperature. The errors associated with ρ and HV are smaller than ±0.002 g cm−3 and ±0.18 GPa, respectively.

531.9 eV. The fractions of the as-prepared and densified glasses constraints for the as-prepared glasses. We thus calculate nc of
are summarized in Table 2. In general, the densification leads to the compressed samples based on the variation in hardness
an increase in the fraction of bridging oxygens, that is, an between the compressed and the as-prepared glass by assuming
increase in the degree of connectivity of the phosphate or a linear scaling between the pressure-induced increase in
silicate network. However, each pressure treatment induces hardness and nc. The calculated nc values for the compressed
different structural changes depending on the glass composi- glasses are given in Table 1. Both the as-prepared and
tion. We discuss the pressure dependence of the number of compressed P and SiP glasses are flexible, whereas the BSi
bridging and nonbridging oxygens for each glass composition and AlBSi glasses are stressed-rigid. The as-prepared BP glass
and its relationship with the chemical dissolution behavior in network is isostatic, becoming stressed-rigid upon compression.
Section III.III. III.III. Dissolution Kinetics of Densified Glasses. We test
III.II. Density, Hardness, and Topological Constraints. the chemical durability of the compressed glasses in acidic (pH
The effects of hot compression on density and hardness are 2) and neutral solutions (pH 7). The dissolution rates of the as-
illustrated in Figure 2a,b, respectively. Data are also prepared glasses in these solutions have already been
summarized in Table S1 in the Supporting Information. Figure determined in our recent study.25 Because of the large number
2a shows an increase in density with increasing applied pressure of durability experiments (three densified glasses for each glass
at Tg, as observed previously in refs12, 13, 29. A similar increase composition in two solutions), we here show only the weight
with the applied pressure is also observed in hardness (Figure loss normalized by the initial surface area as a function of time
2b). The magnitude of the increase in hardness is composition- for the densified SiP glasses (Figure 3). The results for the
dependent as a result of the different pressure-induced remaining four glass compositions are shown in Figures S6−S9
topological changes. in the Supporting Information. Dissolution in aqueous
Following Maxwell’s stability criterion,36 an atomic network solutions can occur through various processes, comprising
can be classified as flexible if nc (number of atomic constrains hydrolysis, hydration, or ion exchange. Processes involving
per atom) <3, stressed-rigid for nc > 3, or isostatic for nc = 3. In diffusion or leaching of cations are associated with a square root
our recent study,25 we have enumerated the value of nc for the time dependence, whereas processes such as hydrolysis exhibit
present glasses based on detailed structural information to a linear time dependence.21 In Figure 3 and Figures S6−S9 in
explain the trend in chemical durability. However, such the Supporting Information, we observe a linear increase of
information is not available for the compressed glasses in this weight loss with dissolution time, with some initial nonlinearity
work and we therefore apply an alternative approach to obtain at short time, which suggests that surface hydrolysis is rate-
nc of the compressed glasses based on the measured hardness limiting. Over the immersion time, each solution remains far
data. Hardness has been shown to scale linearly with nc in from saturation and no plateau in the weight loss versus time
various oxide glass systems,32−35 and Figure S5 in the curve is observed, that is, the kinetics of the dissolution is
Supporting Information indeed shows a direct relationship controlled by only the structural and topological changes with
between the measured hardness and the calculated number of glass composition and pressure.
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Figure 3. Weight loss (in mg dm−2) of the densified SiP glass as a function of time (t in h) under different conditions: (a) pH 2 for P = 0.5 GPa, (b)
pH 7 for P = 0.5 GPa, (c) pH 2 for P = 1.0 GPa, (d) pH 7 for P = 1.0 GPa, (e) pH 2 for P = 2.0 GPa, and (f) pH 7 for P = 2.0 GPa. Two repeated
experiments are performed for each combination of glass, solution pH, and pressure. The dashed lines represent linear fits to the data.

Figures 4 and 5 show the pressure and pH dependence of the P − O − B + H 2O → P − OH + B − OH (2b)

logarithmic dissolution rate, Dr, for all of the compressed
glasses. Dr is calculated from the slope of linear fits to the In acidic solutions (pH 2), reaction 1a,b is favored as the ion-
weight loss curves in Figure 3 and Figures S6−S9 in the exchange step is a process of protonation of phosphate chains,
Supporting Information. The dissolution mechanism of the and a higher concentration of H+ is presented in the aqueous
phosphate-based glasses could be explained through the solutions
reactions of ion exchange (1) and hydrolysis (2).25 In neutral P − O− − M+ + H+ → P − OH + M+ (3a)
solution, there is an equilibrium between the concentrations of
H+ and OH−, that is, both protonation and hydrolysis are P − (O−)2 − M2 + + 2H+ → P − (OH)2 + M2 + (3b)
strongly coupled, and the possible reactions are
As for phosphate network glasses, the dissolution mechanism of
P − O− − M+ + H 2O → P − OH + M+ + OH− (1a) silicate-based glasses could be explained through the reactions
of ion exchange (4a,b and 5a,b) and hydrolysis (6) for neutral
P − (O−)2 − M2 + + 2H 2O (pH 7) and acidic (pH 2) solutions25
→ P − (OH)2 + M2 + + 2OH− (1b) (Si, B, or Al) − O− − M+ + H 2O
P − O − P + H 2O → 2(P − OH) (2a) → (Si, B, or Al) − OH + M+ + OH− (4a)

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Figure 4. Pressure dependence of the logarithmic dissolution rate (Dr, in mg dm−2 h−1) for different flexible and isostatic samples: (a) P glass at pH
2, (b) P glass at pH 7, (c) SiP glass at pH 2, (d) SiP glass at pH 7, (e) BP glass at pH 2, and (f) BP glass at pH 7. Dissolution data for the as-prepared
glasses are also included and taken from ref24.

(Si, B, or Al) − (O−)2 − M2 + + 2H 2O (M+ or M2+, respectively) close to NBOs and the protons (H+)
is preferred in acidic media (reactions 3a,b and 5a,b). However,
→ (Si, B, or Al) − (OH)2 + M2 + + 2OH− (4b) nucleophilic attack (reactions 2a,b and 6) or the breaking of P−
O−P, Si−O−Si, B−O−P, Al−O−Si, or B−O−Si bonds is
(Si, B, or Al) − O− − M+ + H+ associated with the network cross-linking, that is, with a higher
→ (Si, B, or Al) − OH + M+ (5a) degree of polymerization network, and the nucleophilic attack
or the diffusion of water to break bonds is more impeded.
(Si, B, or Al) − (O−)2 − M2 + + 2H+ Figure 4 shows a general enhancement of the corrosion
resistance at both pHs 2 and 7 (i.e., Dr decreases) of the
→ (Si, B, or Al) − (OH)2 + M2 + (5b) phosphate-based P, SiP, and BP glasses following permanent
densification. Figure 4a,b shows the same trend of corrosion
Si − O − (Si, B, or Al) + H 2O → 2(Si, B, or Al) − OH behavior for the P samples in acidic and neutral media. The
(6) compression up to 1 GPa leads to an improvement of chemical
The protonation reactions (1a,b and 4a,b) or the ion exchange durability due to an increase of atomic packing density, as a
between the network modifier alkali or alkaline earth cations consequence of the decrease of the average bond angle and
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Figure 5. Pressure dependence of the logarithmic dissolution rate (Dr, in mg dm−2 h−1) for different stressed-rigid samples: (a) BSi glass at pH 2 (a),
(b) BSi glass at pH 7, (c) AlBSi glass at pH 2, and (d) AlBSi glass at pH 7. Dissolution data for the as-prepared glasses are also included and taken
from ref24.

void volume,19,20 and a decrease in the number of NBOs (see (Figure 4f), and the high influence of the number of NBOs is
Table 2), that is, a higher phosphate network connectivity. clear for acidic solutions (Figure 4e). We note that in Figure 4f
However, when the P glass is compressed at 2.0 GPa, the the change in Dr with pressure is significantly smaller than that
number of NBOs is higher than that at 1.0 GPa, leading to a for P (Figure 4b) and SiP glasses (Figure 4d). This could be
smaller increase in chemical durability from 1.0 to 2.0 GPa because the modifier cation in BP glasses is calcium, which
relative to that from 0 to 1.0 GPa. The Dr and NBO values of diffuses more slowly compared with sodium.3 The larger
the P glasses exhibit the same trend, with the 1.0 GPa sample influence of nucleophilic reaction 2b relative to that of ion-
exhibiting the lowest Dr and NBO value. This result points to exchange reaction 1a,b is confirmed by the leaching of calcium
the importance of the ion-exchange process, that is, the impact cations (see Table S2 in the Supporting Information). That is,
of the NBOs on corrosion behavior, which is also observed in the concentration of leached Ca2+ is lower than that calculated
Figure S10a in the Supporting Information. On the other hand, assuming congruent modifier dissolution, indicating that the
the faster protonation reaction at pH 2 is verified through the modifier dissolution is not congruent and diffusion process 1a is
results of the leaching study (Table S2 and Figure S11 in the slower than hydrolysis process 2b. On the other hand, the small
Supporting Information). A higher concentration of sodium is changes in Dr of BP glass after densification could also be
measured in the pH 2 solution compared to that in pH 7 related to the changes in the boron species. In B2O3-containing
solution, implying that the rate of the diffusion process 1 is glasses,12 it is observed that the densification is accompanied by
faster for lower pH. Moreover, the concentrations of Na+ the partial transformation of B3 to B4. In borate glasses,20 it has
measured by AAS and those calculated by assuming congruent been shown that the lowest Dr is associated with the highest
dissolution are fairly similar (see Table S2 in the Supporting fractions of tetrahedral boron.
Information), indicating that the P glasses exhibit congruent For the densified silicate-based BSi and AlBSi glasses (Figure
dissolution of modifiers. 5), the stressed-rigid networks limit the diffusion of water
The densified SiP glasses (Figure 4c,d) also exhibit lower across the glass. The nucleophilic attack in pH 7 media
dissolution rate values, which align with the pressure depend- (reaction 6) becomes predominant in samples with a higher
ence of fraction of NBOs and density. The densified BP degree of network cross-linking, whereas ion-exchange process
samples (Figure 4e,f) with stressed-rigid networks (nc > 3) 5a is preferred for acid media and in turn influenced by the
show more impeded water attack due to the higher network number of NBOs. Figure 5a reveals an increase in dissolution
connectivity, and the kinetics of dissolution is thus controlled rate at pH 2 upon compression at 0.5 and 1.0 GPa of the BSi
by nucleophilic attack (reaction 4b). Therefore, the Dr is almost glass as a consequence of the increase of the fraction of NBOs
constant for all densified BP samples under neutral conditions (see Table 2). On the other hand, Figure 5c shows a
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Figure 6. Logarithmic dissolution rate (Dr, in mg dm−2 h−1) of the densified oxide glass compressed at (a) 0.5 GPa, (b) 1.0 GPa, and (c) 2.0 GPa as
a function of the calculated number of constraints per atom (nc) in aqueous solutions with pHs 2 and 7. The dashed lines are drawn as guides for the
eyes. Insets: Dr on a linear scale as a function of nc and pH. Error bars are of the size of the symbols.

continuous improvement of dissolution resistance at pH 2 with numbers that contribute to larger nc values, because the nc
increasing pressure for the AlBSi glass. This is due to a lower values are extracted from the measured hardness data. The
fraction of NBOs upon compression, combined with the strong correlation between network topology and the resistance
increase of density. The results of the leaching study confirm of the glasses to water attack is illustrated in the universal plot
that the protonation reaction is preferred for pH 2 (Table S2 in of ln Dr versus nc in Figure 7, which highlights that the network
the Supporting Information). In neutral solutions (Figure
topology controls the majority of the variation in dissolution
5b,d), Dr decreases from as-prepared to densified glass due to
the higher density and network cross-linking for both BSi rate, independent of whether nc is changed by compositional
(Figure 5b) and AlBSi (Figure 5d) glasses. This could be also design or hot compression. The hot-compression process in
due to the pressure-induced changes in the aluminum and
boron speciation through the transformations of B3 to B4 or Al4
to Al5/Al6.12,13
III.IV. Correlating Network Topology and Dissolution
Kinetics. We have previously shown that the dissolution rate
scales with nc for the as-prepared glasses in this study.25 Now,
we test whether this scale also holds for the compressed glasses.
To this end, log Dr is plotted as a function of nc for the glasses
compressed at 0.5, 1.0, and 2.0 GPa in Figure 6. A direct
relationship between the dissolution rate and nc is observed for
all densified glasses in both acidic and neutral pH media at the
various pressures. The insets in Figure 6 show the nc
dependence of Dr on a linear scale, clearly highlighting the
difference in Dr among the flexible and stressed-rigid networks.
In Section III.III, we have discussed the influence of NBOs and
atomic packing density on Dr, but we note that these two
Figure 7. Dependence of the natural logarithm of the dissolution rate
factors cannot alone explain the pressure dependence of Dr, as (Dr, in mg dm−2 h−1) in different aqueous solutions (pHs 2 and 7) on
shown in Figures S10 and S12 in the Supporting Information, the number of atomic constraints per atom (nc) of the as-prepared and
respectively. On the other hand, the network topology captures densified oxide glasses (0−2.0 GPa). The data for the as-prepared
the full details of the atomic structure following densification, glasses are taken from refs32−35. The two dashed lines indicate the
including the pressure-induced increases in coordination master curves for dissolution at pHs 2 and 7, respectively.

9070 DOI: 10.1021/acs.jpcb.7b04535

J. Phys. Chem. B 2017, 121, 9063−9072
The Journal of Physical Chemistry B Article

oxide glasses leads to general improvement of chemical

properties (Figures 4 and 5), as well as mechanical properties
(Figures 2). The reported nc−Dr relations in Figure 7 could
open up for the atomistic design of new oxide glasses with a
specific hardness bulk dissolution rate for a determined pH
value.
As discussed in Section III.III, the dissolution in the different
types of oxide glasses involves different reactions, which could
occur individually or in combination, depending on pH. To
understand the origin of the nc−Dr relations in Figure 7, we
next consider an energy landscape point of view. Each
topological constraint creates an energy minimum inside the
energy landscape, whereas internal degrees of freedom (3 − nc)
induce the formation of channels between these energy
minima,37 allowing atomic reorganizations with low energy Figure 8. Energy barrier needed to break a unit constraint (E0) as a
barriers. To determine this energy barrier, we consider an function of solution pH and pressure. E0 is determined by fitting the
Arrhenius-like relation of the form24 data in Figure S13 in the Supporting Information to eqs 7 and 8.
⎛ E eff ⎞
Dr = Dr,0 exp⎜⎜ − a ⎟⎟
⎝ RT ⎠ (7) mechanism controlling the kinetics of dissolution with the
where R is the gas constant, T is the temperature, and Dr,0 is a reactions of hydrolysis and ion exchange occurring more in
rate constant that depends on the solution phase chemistry, combination when the pressure reaches 2.0 GPa, as the
yielding the barrierless dissolution rate of completely difference between E0 in acidic and neutral solutions is
depolymerized glass with nc = 0. Eeff significantly smaller at 2.0 GPa pressure than under ambient
a is the effective activation
energy given as24 conditions.

Eaeff = ncE0 (8) IV. CONCLUSIONS

The dissolution kinetics of different phosphate- and silicate-
where E0 is the energy barrier that needs to be overcome to
based densified glasses has been studied by measuring the
break a unit atomic constraint. Here, we are considering
weight loss and modifier leaching concentrations of bulk
isothermal dissolution and E0 is therefore determined from the
samples immersed in acid (pH 2) and neutral (pH 7) media.
slope of linear evolution of the logarithmic dissolution rate with
Supplementary density, hardness, and XPS measurements have
respect to nc (see Figure S13 in the Supporting Information).
also been performed. The hot compression treatment leads to a
The values of Eeffa are summarized in Table 3, and the fitted
general improvement of the chemical durability, which is found
to be directly correlated to the increase in network rigidity. The
Table 3. Effective Activation Energy (Eeff
a ) for Dissolution of activation energy to break a unit constraint during dissolution,
All of the Compressed Samples at pHs 2 and 7 which is an indicator of the dissolution mechanism, is always
−1 found to be lower at pH 2 than at pH 7 independent of the
effective activation energy, Eeff
a (kJ mol )

compressed at 0.5 GPa compressed at 1.0 GPa compressed at 2.0 GPa

applied pressure, highlighting the universal topological control
of dissolution. With this research and existing topological
nc (−) pH 2 pH 7 nc (−) pH 2 pH 7 nc (−) pH 2 pH 7
models, it is thus possible to design new oxide glasses with a
2.84 27.1 49.3 2.86 24.5 49.5 2.84 29.7 45.3 specific chemical durability based on a combination of
2.96 28.2 51.4 2.98 25.5 51.6 2.90 30.3 46.3 compositional tuning and hot compression post-treatment.
3.06
3.50
3.73
29.2
33.4
35.6
53.1
60.8
64.8
3.09
3.53
3.76
26.4
30.2
32.2
53.5
61.2
65.1
3.13
3.54
3.92
32.7
37.0
41.0
50.0
56.5
62.6
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcb.7b04535.
values of E0 are plotted against the applied pressure in Figure 8
for pHs 2 and 7. In general, the activation energy is lower in O 1s core-level XPS spectra of as-prepared and
acidic solution compared to that in neutral pH solution as the compressed samples at 0.5, 1.0, and 2.0 GPa; hardness
ion-exchange process involves local deformation of the of as-prepared samples as a function of the number of
network, which should be associated with lower activation atomic constraints per atom; weight loss curves for the
energy. Hydrolysis involves the breaking of bonds and thus compressed P, BP, BSi, and AlBSi glasses in different pH
higher activation energy. As expected, this infers that the solutions; dependence of the dissolution rate on the
dissolution by hydrolysis is predominant for pH 7, whereas ion pressure-induced changes in density and fraction of
exchange is predominant at pH 2. Considering the error range NBOs; atomic constraint dependence on dissolution
of the data, E0 appears to remain constant with pressure (at rate; concentrations of leached sodium and calcium ions;
least up to 1.5 GPa) at each pH value, confirming the universal density and hardness values of densified glasses (PDF)
topological control of dissolution discussed above. However, we
note that E0 slightly decreases and increases when the applied
pressure reaches 2.0 GPa in pH 2 and pH 7 solutions,
■ AUTHOR INFORMATION
Corresponding Author
respectively (Figure 8). This could indicate a change in the *E-mail: [email protected].
9071 DOI: 10.1021/acs.jpcb.7b04535
J. Phys. Chem. B 2017, 121, 9063−9072
The Journal of Physical Chemistry B Article

ORCID (16) Uhlmann, D. R. Densification of Alkali Silicate Glasses at High

Morten M. Smedskjaer: 0000-0003-0476-2021 Pressure. J. Non-Cryst. Solids 1973, 13, 89−99.
(17) Yamada, A.; Gaudio, S. J.; Lesher, C. E. Densification of MgSiO3
Notes Glass with Pressure and Temperature. J. Phys.: Conf. Ser. 2010, 215,
The authors declare no competing financial interest. No. 012085.

■
(18) Guerette, M.; Ackerson, M. R.; Thomas, J.; Yuan, F.; Watson, E.
B.; Walker, D.; Huang, L. Structure and Properties of Silica Glass
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9072 DOI: 10.1021/acs.jpcb.7b04535

J. Phys. Chem. B 2017, 121, 9063−9072