Journal of Non-Crystalline Solids 358 (2012) 2847–2854

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Journal of Non-Crystalline Solids

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Chemical durability and weathering resistance of canasite based glass and

glass-ceramics
Wei Deng a, Jin-shu Cheng a,⁎, Pei-jing Tian a, Mi-tang Wang a, b
a
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan, 430070, China
b
School of Material and Metallurgy, Inner Mongolia University of Science and Technology, Baotou, 014010, China

a r t i c l e i n f o a b s t r a c t

Article history: Classic composition 8.4Na2O·5K2O·10.8CaO·64SiO2·10.5CaF2·1.3Al2O3 (G1/GC1) and high silicon composition
Received 27 March 2012 7.6Na2O·4K2O·8.4CaO·71SiO2·8CaF2·1.0Al2O3 (G2/GC2) canasite-based glass and glass-ceramics were pre-
Received in revised form 2 July 2012 pared, and the chemical durability and weathering of samples were studied with XRD, ICP-AES, SEM and optical
Available online 2 August 2012
microscopy. Interestingly, a kind of color fringe pattern caused by the acid leaching was directly observed on the
glass ceramic surface under optical microscopy. The 20 day weight losses of glass and glass ceramic in acid (1 M
Keywords:
Glass-ceramics;
HCl) and alkali (1 M NaOH/1 M Na2CO3) solution were measured. Accelerated weathering was used to demon-
Chemical durability; strate that increasing silicon content contributes to the weathering performance of glass and glass-ceramics. For
Weathering resistance; different micro-structures and compositions, the weight loss of each glass and glass-ceramic is quite different. In
Canasite general, through increasing the network interconnectivity of residual glass network and suppressing the crystal-
lization of the less durable canasite phase, the addition of SiO2 (from 60 mol% to 71 mol%) enhanced the chem-
ical durability of canasite-based glass and glass ceramic relatively under acid, alkali and weathering conditions.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction surface morphology in corrosive environment or the weathering re-

Glass-ceramic is popular as a building material due to its good me-
chanical properties, excellent chemical durability, and esthetic ap-
pearance [1]. The chemical durability of architectural glass or
glass-ceramic is an important property affecting their service perfor-
mance since they are constantly exposed to natural circumstances [2].
For the interlocking micro-structure of canasite phase [3], this kind of
glass ceramic has high biaxial flexural strength and fracture tough-
ness (KIC = 3–5 MPa·m 1/2 [4]). In application, the soft translucence
of the basic white, opaque canasite-based glass ceramic, perceived
by architects and designers as having a marble-like “depth”, serves
as a building material with excellent mechanical properties [5,6].
With different colorants, it has a wide range of available strong bright
colors in addition to white. So it can be utilized for commercial floor
tiles or wall decoration materials [6]. But at relatively low content of
silica (60 mol%), this material is inferior in acid resistance to soda–
lime glass [5]. In order to improve its chemical durability, Anusavice
and Zhang [7,8] increased the Al2O3 content of canasite-based glass
ceramic and tested its chemical solubility in 4% HAc (ethanoic acid)
and pH 1 buffer solution; Stokes et al. [9] also investigated the effect
of mixed-alkali on the chemical solubility of fluorcanasite forming
glasses. But all these efforts were made to develop a new kind of den-
tal ceramic under standard dental material requirements. As far as we
know, there are no similar investigations such as the appearance of
⁎ Corresponding author. Fax: +86 27 87860801.
E-mail address: dengwei@whut.edu.cn (W. Deng).
sistance of architectural canasite based glass-ceramics.
As is well known, a high silica content has a tendency to improve
glass-network interconnectivity and enhance chemical resistance of
glass by increasing the ratio of bridging oxygens and nonbridging ox-
ygens. In the present work, we characterized a high content silica
(71 mol%) canasite-based glass and glass ceramic and compared
them with the classical chemical composition (61 mol%) [3]. The ob-
jective of the present study was to analyze the effect of silica content
change on the chemical durability and microstructure of canasite
based glass and glass ceramic in 1 M HCl solution, mixture solutions
of 1 M NaOH/1 M Na2CO3 and weathering condition.
2. Experimental
2.1. Synthesis of glass
Glasses with nominal composition of 8.4Na2O·5K2O·10.8 CaO·64
SiO2·10.5 CaF2·1.3Al2O3 (G1) and 7.6Na2O·4K2O·8.4CaO·71SiO2·8
CaF2·1.0 Al2O3 (G2) were prepared from high purity SiO2, CaF2,
CaCO3, Na2CO3, K2CO3 and Al2O3. Na2CO3. The glasses were prepared
by melting 100 g in an electric furnace (Nabertherm Model HT40117)
at 1400 °C/2 h in a platinum crucible. The first hour of the melt was
static to allow initial melting of the batch. Then the melts were stirred
by a platinum paddle at approximately 45 rpm for 50 min to homo-
geneity. The melt was poured into a pre-heated stainless steel mold
to form, and then annealed to reduce internal stress. Cast samples
were cut into 2 × 15 × 20 mm regular bulks for the test of chemical

0022-3093/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2012.07.003
2848 W. Deng et al. / Journal of Non-Crystalline Solids 358 (2012) 2847–2854

Fig. 1. XRD patterns of GC1, GC2 and G1 (with 20 wt.% internal standard Al2O3). ■:
JCPDS 45‐1398, Canasite-A; □: JCPDS 77‐2093, Fluorite. syn; △: JCPDS 78‐2427, Alumi- Fig. 3. Mass loss vs. time for different glass samples in 1 M HCl solution at 25 °C. The num-
num Oxide. ber of samples for error analysis is 3 (Na–Ca–Si glass data was taken from Ref. [13]).

Table 1 To characterize crystalline microstructures, samples were polished

Quantitative analysis of crystal phases in glass ceramics. and eroded by HF (2 wt.%) for 10 s for the morphology observation
Residual glass Canasite CaF2 on the FE-SEM (S-4800, Hitachi Ltd., Japan).
wt.% wt.% wt.%

GC1 56.4 38.4 5.2 2.2. Leaching test

GC2 65 30.7
stability and weathering. The densities of different parts of each cast
sample were measured to guarantee the homogeneity of the matrix
glass.
Part of each sample was nucleated and crystallized at the tem-
peratures (GC1: 530 °C/1 h and 850 °C/1 h; GC2: 550 °C/1 h and
870 °C/1 h) chosen based on the DTA measurement (NETZSCH
STA449C). All the samples were labeled as G1, G2, GC1 and GC2 to indi-
cate the glasses and glass ceramics respectively.
Acculab® ALC-210.4 analytical balance (Germany, accuracy:
0.0001 g) with attachments was used to measure the density of sam-
ples (repeated 3 times, the final measurement result was the average).
X-ray diffraction (XRD) measurements were performed in a D/Max-IIIA
X-ray diffractometer (Rigaku Corporation, Tokyo, Japan) with CuKa ra-
diation. The step-counting parameters used were as follows: start
angle, 60.0°; finish angle, 10.0°; step interval, 0.02°. Data were analyzed
using MDI Jade 5.0 software.
The amount of crystalline Canasite and CaF2 was determined using
the method devised by F. H. Chung [10]; 20 wt.% Al2O3 was used as
the internal standard. The amount of residual glass was determined
by the Rietveld-based method of DOC [11].
4.3
In order to evaluate the chemical stability and weatherability of the
glasses and glass-ceramics, experiments on the chemical stability and
weathering of samples were performed. Before these tests, the regular
glass and glass ceramic samples (2× 15× 20 mm) were polished with
PowerPro 4000 apparatus; Buehler® Metadi® monocrystalline dia-
mond suspension was used in polishing. In reference to the architectur-
al standard (JC/T 872‐2000) for glass-ceramics [12] and the leaching
test [13] made, all samples (G1, G2, GC1 and GC2, the number of parallel
samples for error analysis was 3) were placed in Teflon containers with
50 ml acid (1 M HCl) or alkaline (mixture of 1 M NaOH and 1 M
Na2CO3 with same volume) solution respectively at 25 °C (regulated
with a thermostat) for 20 days, and the glass surface area/solution vol-
ume ratio is about 15/1 (mm 2/ml). At a fix time (5 day) interval, sam-
ples were removed from the solution, rinsed, dried at 100 °C,
weighed, and then placed in the respective solutions again. An
ALC-210.4 analytical balance was used to measure the weight of the
samples. The final result of each sample was the average of 3 repeated
measurements. The chemical durability of the glass and glass ceramic
samples was expressed by weight loss per surface unit in different solu-
tions. To guarantee that the movement of samples in the weight mea-
surement had little influence upon result, the acid and alkaline
leaching solutions after 5, 10 and 15 days (samples were kept all the

10.0µm 10.0µm
GC1 GC2

Fig. 2. SEM images of the etched section of GC1 and GC2 glass-ceramics (2% HF, 30 s).
 W. Deng et al. / Journal of Non-Crystalline Solids 358 (2012) 2847–2854
Fig. 4. Mass loss vs. time for different glass samples in alkaline solution at 25 °C. the
number of samples for error analysis is 3 (Na–Ca–Si data was taken from Ref. [13]).
time in contact with the leaching solution) were also analyzed in order
to detect the concentration of elements of glasses by ICP-AES (Optima
4300DV, Perkin Elmer Ltd., USA). These solutions were filtrated and di-
luted in acid medium (about 5% HNO3) before the ICP-AES test; the in-
strument error is about ±1.5–2%. In addition, the superficial decay of
the surface was directly observed by optical microscopy (Model
VHX-600K, KEYENCE, Osaka, Japan).
Furthermore, samples were submitted to an accelerated weathering
test under specific conditions: temperature equal to 75 °C (regulated
with a thermostat) and relative humidity equal to 75% (regulated
with a humidistat) on the basis of previous studies [14,15] for
13 days, and the distilled water was used in the aging cycle. According
to the method provided by the report of the International Commission
on Glass (Sub-Committee A2) [16], the amount of alkali extracted on
the weathering glass and glass ceramic surface was estimated by
G1
G2
Fig. 5. Optical microscopy images of sample surfaces after polished.
2849
using ICP-AES to analyze the dealkalization solution. A commercial
Na–Ca–Si system plate glass was also tested as a control material. Scan-
ning electron microscopy equipped with an energy dispersive X-ray
spectrometer was used to undertake a detailed study of the surface
morphology and chemical composition.
3. Results
3.1. Glass and glass ceramic phase analysis
The densities of G1, G2, GC1 and GC2 are 2.5138 g/cm 3,
2.5848 g/cm 3, 2.4675 g/cm 3 and 2.5347 g/cm 3. Obviously, the crys-
tallization of canasite decreases the density. The XRD patterns of
GC1 and GC2 powders (mixed with 20 wt.% Al2O3) are shown in
Fig. 1. Same main crystal phase was presented in GC1 and GC2
with suitable heat treatment schedule, except that the intensity of
XRD peaks in GC1 is higher than that in GC2. It suggests that the
crystal volume of GC1 is more than that of GC2. The diffraction
peaks of GC1 and GC2 can be easily assigned to the crystallization
of canasite (JCPDS No. 45-1398) and CaF2 (JCPDS No. 77-2093).
The quantitative analysis results of the amount of crystal phases
are shown in Table 1; the amount of crystallites in GC2 is less than
that of GC1. So with the content of SiO2 rising by 71 mol%, the crys-
tallization capability of GC2 is weaker than that of GC1. Relatively
high silica content suppresses the crystallization of the canasite
phase.
The microstructures of GC1 and GC2 were investigated by SEM
(Fig. 2). Accordingly, the final GC1 was dense and highly crystalline,
with a plenty of interlocked lath-like fluorcanasite phase. Although
the amount of crystallites in GC2 appeared to be less than that of
GC1, the crystallites in GC2 were still plenty and fine-grained.
3.2. Chemical durability
In Figs. 3 and 4, the weight losses (in μg/mm 2) for samples G1, G2,
GC1 and GC2 in acid and alkaline media at room temperature are
reported with the soda–lime–silica glass as a control material [13].
GC1
GC2
2850 W. Deng et al. / Journal of Non-Crystalline Solids 358 (2012) 2847–2854

K2

K1

G1 GC1

G2 GC2

Fig. 6. Optical microscopy images of sample surfaces contacted with 1 M HCl after 10 days.

These plots are representatives of the average of three parallel sam-
ples, and the value of error bars was the standard error (or Bessel
standard error). The interaction between the leaching medium,
glass surface and network structure was expressed by the weight
loss as a function of time. In Fig. 5, the polished surface images of
glass and glass ceramics are shown by optical microscopy. Figs. 6
and 7 present the optical microscopy images of all glasses and glass
ceramic surface contacted with 1 M HCl and a mixture of 1 M NaOH
and 1 M Na2CO3 with same volume solutions (after 10 days). The
ICP-AES analysis results of leachates in acid and alkaline solutions
after 5, 10 and 15 days are shown in Tables 2 and 3. The concentra-
tions of [Na], [Ca] and [Si] in leachates are given in mg/l. Normalized
releases have been calculated from the relation [17,18] Ni = [i]V/fiS
(where [i] is the i element concentration, fi the weight fraction of

G1 GC1

G2 GC2

Fig. 7. Optical microscopy images of sample surfaces contacted with a mixture of 1 M NaOH and 1 M Na2CO3 after 10 days.
 W. Deng et al. / Journal of Non-Crystalline Solids 358 (2012) 2847–2854 2851

Table 2 is greater than that of G2 and GC2. The ratios of the normalized re-
Results analyses of leachates performed in acid solution at 25 °C for 5, 10 and 15 days. leases of Na/Si are higher than that of Ca/Si, which indicated that
Time (days) [Na] mg/l [Ca] mg/l [Si] mg/l Na/Si Ca/Si the order of preferential releasing element: Na > Ca > Si; the Na/Si
and Ca/Si ratios of G1 and GC1 are greater than that of G2 and GC2 re-
G1 5 12.92 4.96 2.74 21.91 3.75
10 16.70 13.56 7.62 10.16 3.69 spectively, suggesting that the high content of silicon decreases the
15 18.76 13.76 7.75 11.22 3.68 leach of cations in acid solution. It also conforms to the mess losses.
G2 5 8.89 3.65 3.19 15.83 3.39 Firstly, the weight losses of glass ceramics (GC1, GC2) were obvi-
10 13.32 9.74 8.81 8.59 3.27
ously higher than that of glasses (G1, G2) even though the bulk com-
15 15.72 10.45 10.64 8.29 2.91
GC1 5 22.49 13.37 14.63 7.13 1.89 positions are exactly the same. This indicates that the crystallization
10 27.55 17.97 18.33 6.97 2.03 is the major factor affecting the durability of glass ceramics in acid so-
15 29.57 18.01 19.41 7.20 2.02 lution. Through previous studies, fluorcanasite can slowly decompose
GC2 5 17.85 9.04 15.97 6.34 1.68 in acid [19]. It demonstrates that the high weight losses of glass ce-
10 20.71 10.72 18.62 6.31 1.71
ramics are most likely caused by the disintegration of canasite
15 21.96. 11.16 19.57 6.36 1.69
which is exposed on the surface layer and had direct contact with
the acid solution.
Secondly, during exposure to acid or water solution, the different
the i element, V the leachate volume, S the glass surface area), the ra- constituents of glass are usually extracted from the glass at different
tios of the normalized releases can be expressed as Na/Nb = [a]V/faS/ rates [2]. As we know, the content of silica has decisive influence on
[b]V/fbS = [a] fb/[b] fa (a and b are the different elements). the ratios of bridging oxygens and nonbridging oxygens in glass (or
residual glass), and comparing with bridging oxygen which is shared
3.3. Weathering by two [SiO4] tetrahedra, nonbridging oxygen is similarly susceptible
to a penetration of “proton” from water or acid [20,21]. Thus, high silica
In Fig. 9, the amount of alkali extracted on the weathered glass and content has a tendency to increase glass-network interconnectivity and
glass ceramic surfaces after 13 days is reported. Figs. 10 and 11 show increase the chemical durability of glass or glass ceramics in acid. In the
the SEM images of the sample surface (G1, G2, GC1 and GC2) glass dissolution studies of Bunker et al. [22,23], the mono- and divalent
subjected to weathering at 75 °C and 75% RH for 13 days; the EDS mi- cations are leached from the glass surface by exchange with protons in
croanalysis results are also included. the solution in the early stage of the reaction. These metal–proton
exchange reactions result in the glass network hydrolysis and formation
of a surface layer rich in Si which has a composition different from that
4. Discussions
of the bulk glass; the thickness of the layer increases with time. In the
case of more durable glasses such surface layer decreases the dis-
4.1. Chemical durability
solution rates of glass constituents and can eventually stop leaching of
glass in acid or water solution. This is the direct cause as the weight
4.1.1. Acidic condition
loss curves rise first then flatten out as time goes by.
The weight losses of glass and glass ceramic samples in 1 M HCl
In the experiment in acid solution, although the crystallization of
solution at room temperature are shown in Fig. 3. All curves first
canasite has a predominant influence in resistance against acid, the re-
rise then flatten out as the test progresses. The weight loss of canasite
sults of weight loss and ICP-AES analyses suggest that high silica content
composition glass (G1, G2) is a little higher than that of Na–Ca–Si
glass or residual glass does have better durability against acid attack.
glass. But the dissolution rates of glass ceramics (GC1, GC2) in HCl so-
At last, the composition changes in the residual glass caused by the
lution are significantly higher than that of glasses (G1, G2). In addi-
precipitation of canasite should not be ignored. The bulk glass of GC1
tion, high silica content shows better durability against acid attack
has a composition very close to that of stoichiometric canasite (Na4K2-
(the weight lose of G1 > G2, and GC1 > GC2).
Ca5Si12O30F4) with an excess amount of CaF2 [3]; the process of crystal-
In order to investigate the leachates in acid solutions, the ICP-AES
lization does not change the residual glass composition. However, as the
analysis result of leachates performed in acid solution at 25 °C for 5,
silica content of bulk composition is higher than that of stoichiometric
10 and 15 days is listed in Table 2; the Na/Si, Ca/Si ratios for the sam-
fluorcanasite, the crystallization of fluorcanasite in GC2 increased the
ples are also included. The concentration of ions increases with time
concentration of silicon in the residual glass. Accordingly, the chemical
and it should be noticed that the increase of ion concentration from
durability of the resultant glass ceramic can be affected. Thus, as the dif-
10 to 15 days is less than that change from 5 to 10 days, which con-
ference of the silicon concentration in the residual glass between GC2
forms to the weight losses. Generally, the ion concentration of glass
and GC1 is higher than that between G2 and G1, and also the content
ceramic is higher than that of glass; the leaching rate of G1 and GC1
of unstable fluorcanasite in GC1 is higher than that in GC2 (estimated
by XRD, meanwhile G1 and G2 are pure glasses), the weight loss differ-
Table 3 ence between GC2 and GC1 is higher than that between G2 and G1.
Results analyses of leachates performed in alkaline solution at 25 °C for 5, 10 and In order to understand the process of leaching, optical microscopy
15 days. was used to characterize the changes in surface features. For compari-
Time (days) [Ca] mg/l [Si] mg/l Ca/Si
son, the images of sample surface after polishing are shown in Fig. 5.
The morphology of surface crystals on the glass ceramics is clearly visi-
G1 5 10.57 26.74 1.83
ble after polishing.
10 22.29 49.14 1.88
15 28.94 74.16 1.62 The optical microscopy images of samples subjected to acid attack
G2 5 6.76 20.15 1.89 (1 M HCl) at room temperature for 10 days are presented in Fig. 6. It
10 12.31 37.86 1.92 can be seen that the surfaces of G1 and G2 are full of typical vermiform
15 20.18 68.53 1.94
grooves. Particularly, for the high stress concentration the scratches
GC1 5 11.73 23.49 1.96
10 23.12 47.11 2.03 caused by polishing were significantly eroded by the acid solution. In-
15 28.41 76.32 1.72 terestingly, a kind of color fringe pattern was presented on the surface
GC2 5 8.63 18.22 2.80 of GC1 and GC2 after erosion by acid. The appearance of these fringe
10 16.27 33.48 2.87 patterns is quite similar to the canasite crystals in Fig. 5. Obviously,
15 21.73 45.69 2.81
this phenomenon was caused by the decomposition of canasite.
2852 W. Deng et al. / Journal of Non-Crystalline Solids 358 (2012) 2847–2854
polished surface
GC1
Fig. 8. 3D images of GC1 GC2 contacted with mixture of 1 M NaOH and 1 M Na2CO3 after 10 days and the polished surface of glass ceramics before corrosion test.(the biggest fluc-
tuation of the polished surface, GC1 and GC2 is 1.9 μm, 12.7 μm and 13.4 μm respectively).
After the disintegration of canasite in acid solution, from the regular
lath-like microstructure of the canasite phase, lots of parallel grooves
formed on the surface and caused light dispersal under the microscope.
These fringe patterns were directly characterized by the decomposition
of crystal phases on the surface of the glass-ceramics. In the image of
GC2 after leaching (Fig. 6), there is a beam of crystal grown through
the polishing surface at an angle. Part of the crystal (K1) was leached
by acid and color fringe patterns became fully apparent; the remainder
(K2) still enclosed with and protected by the residual glass. This appear-
ance can prove that the residual glass has better durability than canasite
phase in acidic conditions, which can be identified as the main reason
for the low resistance to leaching in acid condition.
Fig. 9. The amount of alkali extracted on weathering glass and glass ceramic surface
(after 13 days of accelerated weathering).
GC2
4.1.2. Alkaline conditions
In Fig. 4, the weight losses of glasses and glass ceramics in a mix-
ture of 1 M NaOH and 1 M Na2CO3 solution at 25 °C for 20 days show
a linear correlation of the time. The resistance of samples against al-
kaline attack increased in the order: GC1 b G1 b GC2 b G2. The
ICP-AES analysis results of leachates performed in the alkaline solu-
tion are reported in Table 3. The leachate concentrations of [Ca] and
[Si] in GC1 and GC2 were higher than that in G1 and G2 respectively;
it suggests that the content of silicon is the major factor to affect the
durability of glass ceramics in the alkaline solution. The Ca/Si ratios
of the pure glassy material (G1 and G2) leachate were smaller than
that of glass ceramics (GC1 and GC2); this indicates that the crystalli-
zation of canasite also has an effect on the durability of the material as
its composition is distinguished from the residual glass.
Both mechanisms—ion exchange and glass network hydrolysis—
exist also in neutral and acid conditions. The specificity of the alkaline
solution is that tetrahedral SiO4 sites common to all silicate glasses
were susceptible to nucleophilic attack primarily by OH− to form a
reactive five-coordinated intermediate which can be decomposed
to rupture the Si\O\Si bond (`Si\O\Si ` + OH− → `Si\O − +
HO\Si`) [24,25]. Therefore, a significant quantity of OH− could im-
prove the formation of a five-coordinated intermediate which could
lead to the collapse of Si–O network and a greater dissolution of glass
into the solution. From the weight loss results, these samples suffered
from poor durability performance under alkaline conditions. The reac-
tion is controlled by a linear time dependence, there is no such
build-up of insoluble reaction products on the surface, and all the
glass components are released in the solution directly [26,27].
Since high silica content has a tendency to increase glass-network
[28], the dissolution rates of G2 and GC2 in the alkaline solution were
decreased. The mass losses of G1 and GC1 were obviously higher than
that of G2 and GC2. Comparatively, the weight loss curve of G1 was al-
most overlapped with that of GC1, which indicated that the crystalliza-
tion of canasite has less effect on the chemical durability of G1/GC1 in
 W. Deng et al. / Journal of Non-Crystalline Solids 358 (2012) 2847–2854 2853

5.00µm 5.00µm
G1 G2

Area 1 in G2 Area 2 in G2

Fig. 10. SEM images of glass samples after weathering and Quantitative EDS scans of the selected area in G2 after weathering.

the alkaline solution. This is also in accord with the result of Si ICP-AES. In order to understand the weathering performance of the canasite
However, according to the Si ICP-AES analysis of G2 and GC2, the disso- compositions in this study, the amount of alkali extracted on the weath-
lution of GC2 is more resistant than G2. ered glass and glass ceramic surfaces was investigated. As shown in
The appearance of samples after leaching was observed by optical mi- Fig. 9, the weathering performance of canasite based glass (G1 and
croscopy and shown in Fig. 7. The result indicated that the decomposition G2) is similar with the Na–Ca–Si system glass. The amount of alkali ex-
of G1 glass sample is more serious than that of G2 glass after 10 days in traction in G1 and GC1 is higher than that of G2 and GC2 respectively.
the alkali solution. The surfaces of glass ceramics (GC1 and GC2) are So, high silica content shows better durability against acid attack. The
completely changed after alteration; canasite phases or altered defects crystallization of canasite increased the amount of alkali extracted on
are barely noticeable in it. So the 3D fine depth image composition was weathering glass ceramic (GC1/GC2> G1/G2); the further analysis on
used to determine the surface topography of GC1 and GC2. Fig. 8 presents it will be given in the next paragraph.
the 3D images of surfaces in contact with mixture alkaline solution after The appearance of samples after weathering was observed by scan-
10 days. Comparing with the polished surface before leaching, many con- ning electron microscopy. As shown in Fig. 10 (a), it can be seen that
cave depressions were present. Unlike that the acid tends to etch canasite after 13 days of weathering, G1 glass weathered more seriously than
phase, the alkaline solution leached the glass and canasite phases on the G2 for less content of SiO2. More white plate crystals and aggregates
surface without distinction. So the sign of canasite phases cannot be dis- precipitated on the surface of G1 than that of G2. In Fig. 10 (b), the
tinguished under optical microscopy (Fig. 7). EDS microanalyses were carried out on different areas of the G2 surface.
The calcium and carbon content of white crystals is higher than the
4.2. Weathering other areas. These precipitations were demonstrated to be calcium car-
bonate (the detailed data are listed in Table 4). After 13 days of
In the previous research, the process of glass weathering has been
divided into four steps [29,30]: 1. Water molecule is attracted on the
Table 4
glass surface and connected with silicon–oxygen unsaturated bonds; The EDS microanalysis results of G2 and GC2 after weathering.
2. Some alkali or alkaline earth ions in glass surface leak into the ab-
sorption water and exchanged with H + or H3O +, which can be Element Area 1 in G2 Area 2 in G2 Area 1 in GC2 Area 2 in GC2
wt.% wt.% wt.% wt.%
expressed as: \Si\O\R + H2O=\Si\OH+ROH or \Si\O\R+ 2H2
O\Si\O\H3O + ROH; 3. As the absorption water on the glass surface C 28.02 11.64 10.54 09.36
O 42.48 51.13 39.53 49.90
is not like the aqueous solution, the hydroxyl ions produced by step 2
F 05.72 06.21 06.10 02.99
cannot be diluted, and a more serious hydrolysis reaction is caused: Na 03.47 05.53 04.51 06.83
\Si\O\Si\ + OH− = \Si\OH+ \Si–O −, the network of glass on Al 00.46 00.88 00.81 01.23
the surface is damaged directly. 4. The formation of weathering prod- Si 06.91 15.53 17.41 18.33
ucts is by reaction between ROH (or R(OH)2) and CO2 in atmosphere: K 00.75 01.36 01.29 01.86
Ca 05.70 01.81 09.26 02.25
2ROH+ CO2 = R2CO3 + H2O or R(OH)2 + CO2 = RCO3 + H2O.
2854 W. Deng et al. / Journal of Non-Crystalline Solids 358 (2012) 2847–2854

GC1 5.00µm GC2 5.00µm

Area 1 in GC2 Area 2 in GC2

Fig. 11. SEM images of glass ceramic samples after weathering and Quantitative EDS scans of the selected area in GC2 after weathering.

weathering at 75 °C and 75% RH, the surface of glass ceramics GC1 and chemical durability of canasite-based glass and glass-ceramic relatively
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