Mechanism of Alteration of The Surface of Lead Crystal Glass in Contact With Food: A Chemical Study of The Surface Layer
Mechanism of Alteration of The Surface of Lead Crystal Glass in Contact With Food: A Chemical Study of The Surface Layer
Mechanism of Alteration of The Surface of Lead Crystal Glass in Contact With Food: A Chemical Study of The Surface Layer
com/science/article/pii/S0169433221033079
Manuscript_37206f5cd25fe8dcaa15471dd1f74860
Mechanism of alteration of the surface of lead crystal glass in contact with food:
Christophe RAPIN1
1
Institut Jean Lamour, University of Lorraine, 2 Allée André Guinier, 54011 Nancy, France
2
European Center for Research and Training in Glass Art, Rue de la Liberté, 54112 Vannes-
le-Châtel, France
* Corresponding author
Abstract:
Lead crystal glass (24 wt% PbO) is one of the tableware materials that can release lead into
the environment. A deep knowledge of the release of lead (Pb) due to food contact is
necessary to control an minimize the human exposure to this heavy metal. The Pb leaching
was characterized by elemental analysis (ICP-AES) of the 4vol.% acetic acid solution to
simulate he food contact versus leaching time. The analysis of the subsurface layer (SIMS,
STEM) allows to understand the change of composition and morphology. After an initial
period of rapid leaching, the diffusion of lead out of the glass slows down, due to the
formation of a blocking barrier of diffusion in the subsurface layer of lead crystal glass.
Experiments, carried out with a D218O solution, highlight the different mechanisms of
hydrolysis, then condensation of the silanol groups, explaining the decrease of the diffusion
reinforced by successive leaching processes or by the storage of lead crystal glass at high
1
© 2021 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
Keywords: lead crystal glass, food contact, leaching, subsurface layer.
2
1. Introduction
Over the past several years, the quantity of heavy metals released into the environment has
been significantly reduced to less than one tenth of the emission levels of the 1990s [1].
Concerning lead pollution, the promotion of unleaded gasoline is the main cause of this
significant reduction. Simultaneously, some industrial processes such as metal refining have
been improved to reduce the heavy metal release. Today, the use of lead compounds and the
presence of lead in everyday objects are increasingly controlled and reduced in order to avoid
lead poisoning through the contact with the skin, drinking fluid or food. Nevertheless, the
lead-enriched glass, called lead crystal glass, is an important material used in the luxury
tableware industry. To meet the required specifications for weight, appearance and sound,
lead crystal glass must have a lead oxide (PbO) content of 24 to 40wt.% of lead oxide (PbO).
Some lead-free crystal glass compositions have been developed for tableware applications,
but their physical and thermal characteristics cause significant changes in glass working
The chemical resistance of glassware in aqueous media, also called hydrolytic resistance, is
usually evaluated by measuring the release of elements after immersion in pure water of glass
powder (obtained after ball milling) at 121°C for 30 minutes: this test is particularly used for
pharmaceutical packaging [3]. However, the chemical stability of ceramic and glass tableware
in contact with food is tested at room temperature in acetic acid solution, which is a more
representative medium for food contact [4]. Actually, the foods or beverages, e.g. fruit juices,
tannins in wine or vinegar in some food preparations, generally cause acidic conditions on the
surface of glassware. The release limit for heavy metals such as lead or cadmium for a raw
material and finished article tested in an acetic acid solution has been set to 4000 mg/L
according to ISO 7086 [5], whatever the ratio of lead crystal area to solution volume.
However, many parameters of the finished article, such as surface area, volume and surface
3
finish have to be considered. Thus, it is very difficult to understand the migration of elements
from the materials and, therefore, to understand their release into the food environment.
Rahimi et al. have extensively studied the degradation of silicate glasses with high lead
content (> 40wt. % PbO) in aqueous media [6-8]. However, these high lead glasses undergo a
particular weathering mechanism due to a connected and dense network of plumbate entities
[9-11]. Palomar et al. show that the dissolution of the plumbate network leads to the formation
of a layer of hydrolyzed silica glass or a layer of silica gel, which is very porous [12].
For commercial lead crystal glasses with lower Pb concentration (24 wt.% PbO), the leaching
kinetics of alkali cations and lead cation from lead crystal glass have been reported in various
glass preparation conditions and for several leachate solutions [13-16]; however, these are
Over the last 20 years, Conradt has reviewed the numerous studies carried out to improve the
understanding of the mechanisms responsible for the deterioration of silica glasses by water
[17]. Three main processes can be considered during glass weathering: (i) hydration related to
the diffusion of water molecules within the glass lattice, (ii) hydrolysis corresponding to the
reaction of metal-oxygen bonds with water to form hydroxyl groups, and (iii) an ion exchange
mechanism between lattice-modifying metal cations and protons or hydronium ions in the
aqueous solution [18]. These diffusion and ion exchange processes lead to the formation of a
subsurface zone or layer also known as the “silica gel layer” or “residual layer”, which is
depleted in alkali metals and lead in the case of lead crystal glass. In borosilicate or soda-lime
glasses, a high content of alkali cations, which create non-bridging bonds in the silica lattice,
appears to create channels for diffusion and hydrolysis and can disintegrate the silicate lattice
Other authors focused on long leaching times (from a few hours to more than 100 days). After
a few hours of immersion in aqueous solution, the subsurface layer was analysed by
spectroscopic methods [15, 20, 21]. Yin could clearly detect the gel layer by metallography on
4
very old lead-silicate glazes on artefacts [22] or on soda-lime glass samples exposed for a
very long time in an air-polluted environment [23, 24]. In the case of food contact, the
formation, the thickness and the composition of the subsurface layer on lead crystal glass are
crucial parameters for determining the behaviour of lead crystal glass in contact with food.
This paper proposes a comprehensive investigation of the leaching process of lead crystal
glass (28 wt.%) in a 4vol.% acetic acid solution. The aim is to propose a mechanism for the
formation of the subsurface layer and to investigate its protective characteristic against lead
release when lead crystal glass is in contact with food or drink. For this purpose, lead crystal
glass samples were prepared by mechanical polishing. After the leaching test, the composition
of the acetic acid solution was determined by Inductively Coupled Plasma Atomic Emission
Spectroscopy (ICP-AES) according to the international standard. In addition, before and after
the leaching test, the chemical composition and morphology of the subsurface layer were
mechanism was determined through the use of D218O tracer during the leaching test. Finally,
the properties of the subsurface layer of leached lead crystal glass samples are discussed in the
2. Experimental
20 kg of lead crystal glass was synthesized by mixing: 11.3 kg of silica (SiO2), 5.9 kg of lead
minium (Pb3O4), 207.4 g of sodium carbonate (Na2CO3), 5.6 kg of potassium nitrate (KNO3),
and 142.7 g of antimony trioxide (Sb2O3) with a batch of raw materials which was placed in
an alumina crucible and melted in a gas melting furnace for 16 h at 1300°C. The lead crystal
glass was cast in a graphite mold and annealed for 4 h at 450°C. The glass blocks were then
5
cut into small samples of 3 cm x 3 cm x 0.5 cm using a water-cooled diamond saw. The
surfaces were polished on a felt wheel under water with cerium oxide powder (powder size:
0.5 - 0.6 µm) to a mirror-like surface. The samples were then cleaned with deionized water,
ethanol (96wt.%) and air dried. The chemical composition of the leaded glass was checked by
the Cameca SX-50 electron probe microanalyzer (analysis voltage: 15 kV, beam intensity: 20
nA). The elements Na and Si were calibrated with an albite standard (NaAlSi3O8), K with
orthoclase (KAlSi3O8), Sb with stibnite (Sb2S3) and Pb with galena (PbS). The homogeneity
of the lead crystal glass was verified by 10 measurements on 5 different samples (average ±
standard deviation). The composition of the synthesized lead crystal samples is detailed in
Table 1.
Lead crystal glass samples were placed in closed polyethylene beakers in a 4vol.% acetic acid
solution at room temperature without stirring. There are only three points of contact between
the sample and the beaker, in order to keep almost all the sample surface in contact with the
solution. The ratio of the glass sample surface area (A = 24 cm2) to the volume of the acid
solution (V = 50 cm3) was approximately 0.5 cm-1, which is approximately the A/V ratio of a
whiskey glass. During the leaching time, a solution sample (1 mL) was collected after
determine the concentrations of Pb and K (Power output: 1150 kW, plasma gas flow rate: 0.50
L.min-1, integration time: 0.5 s, emission wavelengths: 220.353 nm for Pb, 766.490 nm for
K). Calibrations of Pb and K were performed by the external method in a 4vol.% acetic acid
matrix. After the leaching experiments, the samples were rinsed with deionized water and
dried on absorbent paper. The Pb released from the lead crystal glass is expressed as Pb
content per cm2 of exposed surface area, according to the relationship (1):
6
∗ 1000 = ,(1)
/
with the concentration of element i in ppm and the concentration of element i in µg.cm-2,
The leaching experiment with D218O water was performed in a specific microcell with a
volume of acetic acid solution of 150 µL and a lead crystal glass surface area of 5.7 mm2 to
ensure the same surface area per volume ratio of 0.5 cm-1. In this case, the 4vol.% acetic acid
solution was prepared by mixing 1 cm3 of D218O (D: 99at.%, 18O: 95at.%) and 40 µL of pure
Before and after the leaching experiments, the lead crystal glass samples were analysed by
SIMS (Cameca IMS 7F) with a Cs+ ion beam (4 keV and 2 nA) analysing a 60 x 60 µm² area.
For samples enriched in deuterium and 18-oxygen, SIMS analyses were performed at high
energy with a Cs+ beam at 15 keV with a mass resolution of 4004. Crater depths were
measured after analysis by confocal microscopy (GBS extended SmartWLI), and the depth
calibration was calculated assuming a constant sputtering rate. Each elemental depth profile is
an average of three analyses in three different areas of the samples. Prior to SIMS analysis,
the samples were coated with a layer of gold by physical spraying to accurately determine the
start of the sample analysis and the origin of the depth profile. The peak intensity of the
16
atomic mass unit (a.m.u.) fragment corresponding to O-, 28
Si-, 39
K-, 208
Pb-, and 23
Na- was
normalized first to the sum of the intensities of the components of the glass to avoid matrix
effects and then normalized by considering the intensity in the mass of the lead crystal glass at
= ,(2)
∑
7
where is the normalized intensity of fragment a (a = 28Si-, 39K-, 208
Pb- and 23Na-), and
and are the raw intensities measured at a point i of the profiles and at a point p of the
fragment peaks were first normalized to the sum of the intensities and then by considering the
Scanning Transmission electron microscopy (STEM) studies were performed using a JEM -
ARM 200F Cold FEG TEM/STEM under cryogenic conditions (-110°C) operating at 200 kV,
equipped with a spherical aberration (Cs) probe and image corrector (0.12 nm point resolution
in TEM mode and 0.078 nm in STEM mode) and electron scattering X-ray spectroscopy
(EDS). Surface samples were metallized with carbon and platinum, and the thin sections were
prepared with a focused ion beam workstation (FEI Helios Nanolab 600i).
3. Results
In 4vol.% acetic acid solution, the Figure 1 shows the evolution of leached lead and potassium
content per centimetre square of lead crystal versus the square root of leaching time.
For lead, a first evolution is characterized by a linear increase of the leached Pb content as a
function of the square root of time up to 16 h and 3 µg.cm-2. Then, the kinetic of Pb leaching
is strongly reduced and the content of released Pb in the solution reaches 3.5 µg.cm-2 for 48 h
of leaching (Figure 1a). For potassium, the kinetic of released K, displayed in Figure 1b,
reveals only one linear increase, and does not show a drastic reduction with time after
approximately 12 h of leaching.
According to the assumption and calculation of Helebrant et al [25] who consider that the
unstirred solution are equivalent to those of a stirred solution. Consequently, the diffusion
8
coefficient D of the elements K and Pb in lead crystal glass can be estimated by fitting each
linear part of the curves c=f(t1/2) in Figure 1 by the following equation, resulting from the
with cX sol the concentration of X in the solution (g.m-3), cx0 the concentration of X in the solid
lead crystal glass (g.m-3), t the leaching time (s) and D the diffusion coefficient of X in the
sample (m-2.s-1).
In Table 1, the order of magnitude of the diffusion coefficient in lead crystal glass with 24
wt.% PbO is consistent with values previously reported in the literature [15, 25]. During the
first leaching regime, the diffusion coefficients of Pb and K are approximately identical
around
10-20 m2.s-1 at room temperature. During the second leaching regime, the diffusion coefficient
of lead is two orders of magnitude lower, while the diffusion coefficient of K is almost
unchanged.
3.2 Elemental profile of lead crystal glass before and after the leaching test
Before and after the leach test, the lead crystal glass samples were analysed by SIMS as
shown in Figure 2. From the raw elemental depth profile, it can be observed that the elemental
composition of the lead crystal glass surface is clearly affected by the mechanical polishing
process over a depth of about 100 nm (Figure 2a). The gradient of composition, highlighted
by the normalized peak intensities in Figure 2c, reveals the presence of three different zones
in the subsurface. The first zone 1, with a depth of about 3 to 5 nm, corresponds to both the
roughness of the lead crystal glass surface and surface contamination with high carbon
concentration, the latest being revealed by the intensity of the 12C- peak. Then, a second zone
2 with a depth of
gradient of alkali atoms and contains approximately the same Pb content as in the bulk lead
crystal glass but. This zone 3 also contains a slight excess of oxygen and a lack of silicon
compared to the lead crystal glass, revealing that the silica lattice composition is also altered
by leaching. These results demonstrate that mechanical polishing in water modifies the
surface of lead crystal glass and that a leaching process is already occurring during this first
preparation step.
In comparison, the composition gradient of the subsurface zones of the sample leached in
acetic acid is shown in figures 2b and d. The first zone 1, corresponding to the carbon-
contaminated depth, is comparable to the polished sample. However, the zone 2, depleted in
Pb, has a thickness of about 35 nm. The K and Na contents are very low and this zone is
almost free of alkali atoms. The low peak of Na content (at about 15 nm) can be explained by
the possible retention of the Na element in this subsurface layer by the modified silica lattice,
as already mentioned in some cases [25]. The silicon profile clearly shows a concentration
the zone 3 is also characterized by a constant Pb content, equal to that of lead crystal glass,
This type of SIMS elemental profile was also analysed after 48 hours of leaching compared to
the sample leached for 24 hours (Figure 3). In fact, for longer leaching time, the Pb gradient
increases slightly within the lead crystal glass, which is well corroborated by the decrease in
Pb leaching kinetics characterized in the solution analysis in Figure 1a. In contrast, the
concentration gradient of alkali atoms shifts significantly within the lead crystal glass, which
is corroborated with the sharp increase in alkali atoms in the acetic acid solution.
10
After 24 h of leaching in 4vol.% acetic, the STEM micrograph, displayed in Figure 4, shows
the general morphology of the subsurface layer. Under the carbon layer deposited during the
thin section preparation steps (in white), the leached layer is relatively uniform. In the bulk
lead crystal glass, some Pb and K-enriched areas can be detected, which may explain some
As can be seen in Figure 5a, the subsurface layer can be easily divided into two main zones,
which can be correlated to the SIMS elemental profile. The first zone, named zone 2 in the
SIMS profile (Figure 2d), is almost free of Pb and K atoms. Moreover, EDS analysis reveals
that zone 2 is characterized by a relatively high silicon content, as observed on the SIMS
analysis (Figure 5b). In-depth, the glass is not homogeneous, and the heavy atoms (Pb and K)
are segregated into nanoscale nodules. This zone can be attributed to zone 3 of the SIMS
profile. The thickness of zone 3 can be estimated at about 60 nm, using the EDS profile
measured at the nanoscale (Figure 5b). Then, deeper than 100 nm, the lead crystal glass
To understand the leaching mechnaism in the lead crystal glass, the leaching process was
performed in D218O water with 4vol.% acetic acid with the same surface to volume ratio. In
Figure 6a, the SIMS profile of 18O and D fragments clearly shows that deuterium and oxygen
18 penetrate down to about 100 nm depth after 24 hours of leaching. Overall, on the in-depth
profile, the normalized intensity of the peaks shows that deuterium diffuses slightly deeper
than oxygen 18. However, 18O is present in the first 40 nm of depth (zone 2) and the 18OD and
D fragments appear mainly deeper than 30-40 nm in zone 3. A lower deuterium content can
18
be noted in zone 2, especially in the first 20 nm of depth (Figure 6b). The OH fragment is
also detected, as H atoms are initially present in the first hydrated layer during the polishing
step and present in the acetic acid during the leaching process.
11
3.5 Effect of multiple leaching and aging
In practice, lead crystal glassware may undergo several successive acid leaches, due to food
contact, separated by several storage times. Figure 7 shows the evolution of the Pb content
released into an acetic acid solution after leaching every 2 months for 1 year, and then after 6
and 10 months. Initially, all lead crystal glass samples release about 3.1 µg.cm-2 of lead, as
already noted in Figure 1. Then, the Pb release decreases sharply to 0.4 µg.cm-2 from the
second leaching to a value below 0.01 µg.cm-2 after 7 leachings and 12 months of storage at
room temperature. If the second leaching is performed after a longer storage time at room
To accelerate the diffusion phenomena of the elements in the glass, the samples were stored at
100°C and 300°C. But the leaching of lead after an initial leaching process and storage at
room temperature, 100°C and 300°C for 2 months reveals that storage at high temperature
drastically reduces the release of lead from lead crystal glass after an initial leaching (Table
3). From a practical point of view, the successive leaching experiments demonstrate that the
subsurface layer, formed during the first leaching process, can provide an efficient protective
Through the results of this study, the leaching of lead and alkali elements was clearly
confirmed on the polished surface in food contact conditions, in 4vol.% acetic acid. The SIMS
elemental profile and EDS analysis reveal a clear concentration gradient of Pb and alkali
atoms in the lead crystal glass material after 24 hours of leaching. However, silicon and
oxygen concentrations are also clearly affected by the leaching process, demonstrating a
significant change in the silicate lattice. Simultaneously, the incorporation of 18O to a depth of
12
100 nm after 24 h of leaching proves that the leaching process cannot be simply described by
Another possible mechanism is the hydrolysis of the siloxane bonds (Si-O-Si) of the silica
lattice with the help of alkaline anions generated by the ion exchange, following the reaction
scheme:
The latter hydrolysis mechanism explains the rapid leaching of Pb and K in the first hours of
the process due to the depolymerization of the silica lattice, as shown in the Pb leaching
kinetics in Figure 1. This hydrolysis phenomenon has already been observed during the
After the first few hours of leaching, the diffusion of lead in the solution is significantly
reduced and the diffusion coefficient of lead is 2 orders of magnitude lower. SIMS and EDS
profiles reveal that the glass is enriched in silicon in the first 20 nm depth compared to the
deeper leached zone. Furthermore, in the Pb-K-free zone, during D218O experiments, the
deuterium content in the Si-enriched zone is relatively low compared to the deeper leached
zone, which can be explained by the condensation of the silanol group (Si-OH) in acidic
medium into Si-O-Si to form a repolymerized silica network in the gel layer, as a result of the
reaction:
Therefore, the Pb-K-free subsurface zone seems to be gradually transformed into a dense
silica lattice by silanol condensation. In fact, the condensation reaction is induced by the
13
acidic pH of the acetic acid medium [26]. By increasing the contact time with the acetic acid
solution, this zone forms a passive layer acting as a diffusion barrier for lead atoms, as shown
These mechanisms lead to the formation of a complex profile of chemical elements in the
subsurface zone of lead crystal glass. Figure 8 schematize and summarize the evolution of the
elemental profile in three time range: (i) the initial stage after polishing, (ii) then after several
hours of leaching, (iii) then after 24 hours. The reactions scheme proposed to explain this
The protective properties of this diffusion barrier are also demonstrated by repetitive leaching
every 2 months in 4vol.% acetic acid in Figure 7. During the two months of storage at room
temperature, the leaching results show that lead atoms do not diffuse to the surface during the
storage time, and the repetitive contact with the acidic solution tends to increase the protective
character of this subsurface layer. Moreover, if the storage is carried out at high temperature
between two leaches, the release of lead after successive leaches shows that the protective
property of the subsurface layer is reinforced. Indeed, the heat treatment of hydrated silica
glass induces dehydration of the silanol groups to produce strained Si-O-Si siloxane bonds,
which seems to limit the diffusion of lead cations in the solution [27, 28]. However, even at
room temperature, conversion of the silanol groups to siloxane groups is possible on silica
which explains the beneficial effect of room temperature storage on the protective properties
14
5. Conclusion
In the food contact conditions, the leaching of lead and alkali from lead crystal glass is
relatively rapid during the first hours; thereafter, the leaching kinetics slow down
significantly. Leaching in acetic acid medium induces the formation of a complex subsurface
zone free of lead and alkali atoms. Using D218O acid leaching experiments, a two-step
leaching mechanism can be proposed. After an initial rapid leaching of Pb, K by nucleophilic
substitution associated to siloxane hydrolysis, the silanol group can condense to form a
network of siloxane bonds again. The SiO2-enriched underlayer, revealed by SIMS and TEM
analysis, explains the slower lead release for longer contact times in acetic acid. The
15
References
[1] European Environment Agency, European Topic Centre on Air Pollution and Climate
Change Mitigation (ETC/ACM), Air quality in Europe: 2018 report, Publications Office,
[3] ISO 720:2020(en), Glass - Hydrolytic resistance of glass grains at 121 °C - Test method
June 2, 2021).
from crystalware under conditions of consumer use, Food Addit. Contam. 17 (2000)
205-218. https://doi.org/10.1080/026520300283469.
[5] ISO 7086:2019 Glass hollowware in contact with food - Lead and cadmium emission -,
2019.
[6] R.A. Rahimi, S.K. Sadrnezhaad, G. Raisali, A. Hamidi, Hydrolysis kinetics of lead
https://doi.org/10.1016/j.jnucmat.2009.02.028.
[7] R.A. Rahimi, S.K. Sadrnezhaad, G. Raisali, Chemical durability of lead silicate glass in
HNO3, HCl and H2SO4 aqueous acid solutions, J. Non-Cryst. Solids. 355 (2009) 169-
174. https://doi.org/10.1016/j.jnoncrysol.2008.11.001.
[8] R.A. Rahimi, S.K. Sadrnezhaad, Effects of ion exchange and hydrolysis mechanisms on
[9] O.L.G. Alderman, A.C. Hannon, D. Holland, S. Feller, G. Lehr, A.J. Vitale, U. Hoppe,
16
formation in high lead silicate glass, 80PbO-20SiO2, Phys. Chem. Chem. Phys. 15
Plumbate Networks in Lead Silicate Glasses, J. Am. Ceram. Soc. 88 (2005) 2908-2912.
https://doi.org/10.1111/j.1551-2916.2005.00508.x.
[11] I. Ben Kacem, L. Gautron, D. Coillot, D.R. Neuville, Structure and properties of lead
https://doi.org/10.1016/j.chemgeo.2017.03.030.
aqueous and high-humidity environments, J. Am. Ceram. Soc. 103 (2020) 5248-5258.
https://doi.org/10.1111/jace.17202.
[13] A.A. Ahmed, I.M. Youssof, Dissolution of lead crystal glass (24% PbO) in aqueous
[14] A.A. Ahmed, I.M. Youssof, Interaction between lead crystal glass (24% PbO) and acetic
https://doi.org/10.1021/acs.est.6b02971.
3093(98)00580-8.
[18] A.K. Varshneya, M.E. Milberg, Ion Exchange in Sodium Borosilicate Glasses, J. Am.
17
[19] S. Gin, A.H. Mir, A. Jan, J.M. Delaye, E. Chauvet, Y. De Puydt, A. Gourgiotis, S.
Kerisit, A General Mechanism for Gel Layer Formation on Borosilicate Glass under
https://doi.org/10.1021/acs.jpcc.9b10491.
[20] R.G. Gossink, H.A.M. de Grefte, H.W. Werner, SIMS Analysis of Aqueous Corrosion
https://doi.org/10.1111/j.1151-2916.1979.tb18793.x.
https://doi.org/10.1038/s41529-019-0076-3.
[22] X. Yin, Chemical evolution of lead in ancient artifacts -A case study of early Chinese
https://doi.org/10.1016/j.jnoncrysol.2006.01.017.
lead crystal glass: comparison of short-term aqueous and atmospheric alteration at 90 °C,
https://doi.org/10.1002/bbpc.19961000934.
[26] C.J. Brinker, Hydrolysis and condensation of silicates: Effects on structure, J. Non-
[27] T.A. Michalske, B.C. Bunker, Slow fracture model based on strained silicate structures,
18
[28] A.S. D'Souza, C.G. Pantano, Hydroxylation and Dehydroxylation Behavior of Silica
https://doi.org/10.1111/j.1151-2916.2002.tb00303.x.
1576. https://doi.org/10.1021/acs.langmuir.5b04506.
19
Oxides Na2O SiO2 K2O Sb2O3 PbO
mol.%. 0.8 ± 0.05 77.3 ± 0.5 11.1 ± 0.2 0.3 ± 0.03 10.4 ± 0.5
wt.% 0.6 ± 0.04 57.3 ± 0.4 12.9 ± 0.2 0.97 ± 0.10 28.8 ± 1.5
Elements Na Si K Sb Pb
at.% 0.57 ± 0.04 26.7 ± 0.2 7.76 ± 0.16 0.19 ± 0.02 3.60 ± 0.20
Table 1: Composition of lead crystal glass in mol.%, wt.% of oxides and at.% of elements.
a) b)
Figure 1: Evolution of leached Pb (a) and K (b) per cm2 of lead crystal (µg.cm-2) as a function
of the square root of the leaching time in a 4vol.% acetic acid solution at room temperature.
20
Pb K
Table 2: Diffusion coefficients of lead and potassium in lead crystal glass in m2.s-1 estimated
a) b)
c) d)
Figure 2: Depth SIMS elemental profile of as-polished lead crystal glass (a, c) and lead crystal
glass leached in 4vol.% acetic acid solution for 24 h (b, d). Raw peak intensity (a, b) and
21
Figure 3: Comparison of the SIMS elemental depth profile of lead crystal glass leached in a
4vol.% acetic acid solution for 24 h (solid line) and 48 h (dashed line).
Figure 4: STEM micrograph (cryogenic conditions) of a lead crystal glass leached in 4vol.%
22
a) b)
Figure 5: (a) STEM micrograph (cryogenic conditions) of the subsurface layer and (b) EDS
peak intensity versus depth of lead crystal glass leached in 4vol.% acetic acid for 24 hours at
room temperature.
a)
b)
Figure 6: SIMS depth profile of lead crystal glass leached in 4vol.% acetic acid in 98wt.%
D218O solution for 24 h. (a) Raw peak intensity, (b) Normalized peak intensity.
23
Figure 7: Evolution of Pb content released in 4vol.% acetic acid after successive leaching of
temperature).
After 2 months of
0.42 ± 0.04 0.065 ± 0.006 0.010 ± 0.001
storage
Table 3: Comparison of released Pb content (µg.cm-2) in 4vol.% acetic acid after 2 months
24
2 3 Bulk 2 3 Bulk
1 1
Normalized
content Potassium
Normalized
content
Lead
Sodium
Silicon
a)
b)
2 3 Bulk
1
Normalized
content
0 ≈ 40 ≈ 100 Depth / nm
c)
Figure 8: Scheme of the evolution of the composition of the subsurface zone of lead crystal
glass at the initial state (after polishing) (a), after several hours of leaching (b), and after 24 h
of leaching (c) in 4vol.%. acetic acid. (The typical normalized contents are displayed in
function of depth for potassium in red, lead in green, sodium in yellow and silicon in violet)
25