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Thermal Poling of Soda-Lime Silica Glass with Nonblocking Electrodes-Part 1:

Effects of Sodium Ion Migration and Water Ingress on Glass Surface Structure

Article  in  Journal of the American Ceramic Society · April 2016

DOI: 10.1111/jace.14081

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 J. Am. Ceram. Soc., 99 [4] 1221–1230 (2016)
DOI: 10.1111/jace.14081
© 2016 The American Ceramic Society

Journal
Thermal Poling of Soda-Lime Silica Glass with Nonblocking Electrodes—Part
1: Effects of Sodium Ion Migration and Water Ingress on Glass Surface
Structure
Jiawei Luo,‡,§ Hongtu He,§,¶ Nikolas J. Podraza,k Linmao Qian,¶ Carlo G. Pantano,§,‡‡ and
Seong H. Kim‡,§,‡‡,†
‡
Department of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802
§
Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802
¶
Tribology Research Institute, National Traction Power Laboratory, Southwest Jiaotong University, Chengdu 610031, China
k
Department of Physics and Astronomy & Wright Center for Photovoltaics Innovation and Commercialization, The University
of Toledo, Toledo, Ohio 43606
‡‡
Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802

It is generally well known that not only the sodium itself, but windows and containers, high-temperature SO2, and fluoro-
also the non-bridging oxygen (NBO) sites associated with carbon treatments are commonly used during the manufac-
sodium ions are largely responsible for the surface reactivity of turing process to reduce the sodium concentration in the
soda-lime-silica (SLS) glass. Thermal poling can modify the surface region.3–6 Acid treatments and organic coatings can
distribution of sodium in the subsurface region. In this work, a also be applied to further deplete leachable sodium ions or
commercial SLS float glass was thermally poled using non- prevent sodium reactions at the glass surface.7–10 These treat-
blocking electrodes in air. The Na+ – depleted anode surface ments alter not only the sodium ion concentration but also
and the Na+ – gradient cathode surface were characterized the chemical structure of the silicate network in the glass sur-
using a variety of methods to find the compositional, structural face, which greatly affects how the glass surface reacts with
and morphological effects of thermal poling. Of particular sig- the environment, especially water in ambient air.11–13 Thus,
nificance is the use of nondestructive vibrational spectroscopy fundamental surface studies of sodium-containing glasses are
methods, which can lead to new and improved understanding of needed to fully understand and control the surface properties
water interactions with sodium and its sites in the glass. It was of soda-lime glass.14,15
found that during thermal poling, the Na+ – depleted glass net- Recently, thermal poling has been explored as a means to
work on the anode side undergoes condensation reactions of study and alter the mobile ion distribution near the glass sur-
NBO sites accompanied by the increase in concentrations of face.16–18 In this process, a glass sample is heated to a tem-
silanol (SiOH) groups and molecular water species. In con- perature at which network modifier ions have sufficient ionic
trast, silanol and water species do not increase and the silicate mobility in the glass when a high voltage direct current (DC)
network change is negligible in the Na+ – gradient cathode side. bias is applied to move cations from the anode side to the
Vibrational sum frequency generation (SFG) spectroscopy ana- cathode side. When the temperature is lowered while main-
lysis revealed the difference in distributions of hydrous species taining the DC bias, the migrated cations are trapped, form-
in the Na+ – depleted and Na+ – gradient surfaces. The struc- ing an ion depletion layer in the anode-side glass surface and
tural information of the thermally-poled surfaces provides criti- an ion accumulation layer on the cathode-side glass surface.
cal insights needed to understand the mechanical and The electric field gradient in the glass surface subsequently
mechanochemical properties of the Na+ – concentration modi- formed by the ion migration induces a second-order optical
fied SLS glass surfaces reported in the Part 2 companion nonlinearity (SON) effect such as second harmonic genera-
paper. tion (SHG) which is otherwise not expected for amorphous
glass materials.19–21
Although the charge distribution and SON properties of
I. Introduction thermally poled glasses are well documented in the literature,
the chemical structure of the poled glass surface is not fully
C ONTROLLING alkali ion concentrations in the surface
region of silicate glasses is of great interest and impor-
tance for many engineering applications since it plays pivotal
understood.17,22,23 During the poling process, the electric-field
induced migration of sodium ions can result in various struc-
roles in chemical and mechanical properties of glass materi- tural changes in the glass network. In the anode-side glass
als.1,2 In the case of soda-lime glass which is widely used for surface, the sodium ion depletion would leave negatively
charged nonbridging oxygen (NBO) groups. These negatively
charged NBO groups could lose electrons which could be
ejected to the anode, leaving neutral NBO groups. If two
J. Mauro—contributing editor NBO groups are in proximity, they could react to form Si–
O–Si linkages and release oxygen to the environment. When
a nonblocking electrode is used,16 water could ingress into
the sodium depleted surface and react with NBO groups
Manuscript No. 37205. Received July 14, 2015; approved November 15, 2015. forming Si–OH. Then, hydroxide anions would be produced
†
Author to whom correspondence should be addressed. e-mail: [email protected]

1221
1222 Journal of the American Ceramic Society—Luo et al. Vol. 99, No. 4

which could further react with the Si–O–Si network. Other and ethanol, and then by UV-ozone to remove organic con-
cationic species could be formed at the anode surface by ion- taminants on the glass surface before thermal poling. A
ization of gas-phase molecules;24,25 these cations could enter stainless steel plate and a highly oriented pyrolytic graphite
the glass surface to compensate the negatively charged (HOPG) disk were used as an anode and a cathode, respec-
groups produced upon sodium ion depletion. The chemical tively. The electrodes were in physical contact with the glass
environment during the poling also affects the cationic spe- surface by its own weight; thus, there were physical gaps
cies involved in charge compensation inside the glass poled between the electrode and glass surfaces, which allowed the
at the anode side.26 On the cathode side, sodium ions accu- environmental gas species to interact with the surface during
mulate in the glass if a blocking electrode is used.17,27 If a the thermal poling process. The thermal poling temperature
nonblocking electrode is used, sodium ions can exit the glass was held constant at 200°C,24,28 well below the strain point
and be reduced to metallic sodium by electrons at the cath- for this glass (~500°C). The temperature of the sample was
ode, and further react with molecules from the gas phase.28 measured by a thermocouple which was in intimate contact
These poling-induced compositional and structural changes with the cathode (ground electrode). After the sample was
are expected to impact the chemical and mechanical proper- equilibrated at 200°C in ambient air, a + 2 kV DC bias volt-
ties of the poled glass surfaces.29 age was applied to the anode. After a given poling time, the
In this study, the silicate network structure and hydrous furnace temperature was lowered until the cathodic current
species (Si–OH and H2O) in the soda-lime silica (SLS) float decreased below the detection limit of the picoammeter
glass, thermally poled using nonblocking electrodes in air, (Model 487, Keithley Instruments, Inc., Cleveland, OH)
were studied. The nonblocking electrode was used so it could whereas the DC bias was held constant at +2 kV. Figure 1(b)
be easily removed for spectroscopic (Part-1) and mechanical shows an example of the temporal profiles of temperature
(Part-2) studies of the poled glass surface. The chemical com- (T), bias voltage (V), and measured current (A).
position, thickness, and surface roughness of the poled layers After thermal poling, white particulates were observed on
were characterized with cross-sectional energy-dispersive X- the glass surface inside the area contacting the cathode. An
ray (EDX) spectroscopy, spectroscopic ellipsometry (SE), AFM topography image of the particulates on the glass sur-
and atomic force microscopy (AFM). The Si–O–Si network face is shown in the inset of Fig. 2. In SR-IR analysis of this
and amount of hydrous species were studied with specular surface, a sharp peak was observed at ~1430 cm1 corre-
reflectance (SR) and attenuated total reflectance (ATR) infra- sponding to the asymmetric vibrational mode of carbonate
red (IR) spectroscopy. The OH groups (Si–OH and H2O) species (Fig. 2).33 Since the nonblocking electrode geometry
with distinct hydrogen bonding interactions within the poled was used, sodium at the cathode side reacted with CO2 form-
layer were studied with vibrational sum-frequency generation ing sodium carbonate [Fig. 1(a)].34 The white particulates
(SFG) spectroscopy. SFG is another type of SON effect could be removed by simple rinsing with a cotton tip wet
which requires noncentrosymmetry like SHG.30,31 While with water. All cathode-side surfaces described in this paper
SHG is responsive to the overall field gradient without any were cleaned to remove the sodium carbonate deposits prior
molecular specificity, SFG provides molecule-specific infor- to analysis.
mation as it probes vibrational modes of functional The EDX analysis was performed using a FEI Quanta 200
groups.31,32 Based on all results of these analyses, a compre- (FEI Co., Hillsboro, OR) Environmental SEM system to
hensive model is proposed for the structural modifications measure the chemical composition changes in the soda-lime
which occur inside soda-lime glass upon sodium migration silica glass due to thermal poling. Samples were prepared by
via thermal poling. fracturing through the poled area. The samples were ana-
lyzed without a conducting layer deposition and the water
vapor pressure was kept at 100 Pa to mitigate surface charg-
II. Experimental Methods
ing problems.
Thermal poling experiments were performed on commercial Spectroscopic ellipsometry (SE) measurements were per-
soda-lime silica (SLS) float glass (Asahi Glass Co, Tokyo, formed using a single rotating compensator multichannel
Japan) with a thickness of 0.7 mm. The nominal bulk com- ellipsometer (Alpha-SE, J. A. Woollam Co., Inc., Lincoln,
position in weight percentage is 74% SiO2, 13.5% Na2O, NE).35,36 Ellipsometric spectra were collected at a 70° angle
10.5% CaO, 1.3% Al2O3, 0.2% MgO, 0.3% K2O, and 0.2% of incidence and a piece of frosted tape was attached on the
SO3. Only the air-side of the float glass was analyzed. A backside of the measured surface to avoid interference by
schematic diagram of the thermal poling setup is shown in incoherent backside reflections. The ellipsometric spectra
Fig. 1. All samples were cleaned by first rinsing with water were fitted using a least-squares regression with an

Fig. 1. (a) Schematic experimental setup of thermal poling experiment. (b) Graphical illustration of typical poling conditions with respect to the
temporal profiles of temperature (T), bias voltage (V), and measured current (A).
April 2016 Structure of Thermally-Poled Glass 1223

unweighted error function37 to a multiple layer structural Microscope (Bruker, Co.) equipped with a Ge ATR crystal
model with fit parameters defining layer thicknesses, material accessory with 45° incidence angle. The glass surface was
volume fractions, and analytic expressions for the index of pressed to the Ge crystal with a 600 N force. The informa-
refraction (n). A Bruggeman effective medium approximation tion depth of ATR-IR was calculated to be 0.5–0.75 lm in
is used to represent n for composite and interfacial layers.38 the OH stretch region.41
For the interface layers, material fractions were fixed at 0.5 Vibrational sum frequency generation (SFG) spectroscopy
of the overlying and underlying layers. Spectra in n for bulk was employed to identify hydroxyl groups with different
glass, as well as the untreated and anode side surface layers, hydrogen-bonding interactions. The detailed setup of the
were represented using Sellmeier oscillator parameteriza- SFG spectroscopy system is described elsewhere.42 Visible
tions.39 After n for the bulk glass was extracted, it was fixed pulses (532 nm) and tunable IR pulses (2.5–10 lm) generated
in the structural model of the cathode and anode side sam- with an EKSPLA laser system (EKSPLA Co., Vilnius,
ples. A sensitivity limit to differences in n of ~0.002 between Lithuania) were spatially and temporally overlapped at the
adjacent layers was deduced from simulations of ellipsomet- glass surface. The incident angles of visible and IR pulses
ric spectra. were 60° and 56° with respect to the surface normal, respec-
The surface topography and adhesion force map were ana- tively. The SFG signal intensity was normalized with the
lyzed through peak-force tapping mode imaging with an intensities of input visible and IR beams. The polarization
atomic force microscope (AFM; Icon, Bruker, Co., Billerica, combination for the spectra collected was s for SFG signal, s
MA). The deflection sensitivity of the silicon tip and the for visible beam, and p for IR beam (ssp).
spring constant of the cantilever were calibrated before the
test. The surface was precleaned by 200-proof ethanol and
III. Results and Discussion
UV-ozone.
Specular reflectance IR (SR-IR) spectroscopy was per- (1) Chemical Composition and Thickness of the Thermally
formed with a ThermoNicolet 670 FTIR spectrometer (Wal- Poled Surface Layers
tham, MA). All IR spectra were taken at a 40° incidence The atomic concentrations of modifier elements (Na, Ca,
angle. A gold mirror was used as a reference background. Mg, and Al) as well as network atoms (Si and O) were mea-
Note that the shoulder peak at ~1250 cm1 is due to the sured in the outermost 20 lm of the anode- and cathode-side
anomalous dispersion effect of the complex refractive index surfaces after 40 min of poling; these profiles, along with the
in the reflection spectrum (Fig. 2), not an absorption band.40 pristine glass reference profile, are presented in Fig. 3. The
Attenuated total reflectance infrared (ATR-IR) spec- pristine surface showed no concentration gradient near the
troscopy was carried-out with a Bruker Hyperion 3000 surface for all elements of the glass within the spatial resolu-
tion of EDX. The charging-induced signal decay of mobile
sodium ions43,44 was not observed at the edge of the glass
cross section in our EDX measurement condition (water par-
tial pressure = 100 Pa).
On the anode side, the formation of a Na+-depleted layer
was clearly observed [Fig. 3(b)]. For 40 min poling, the
thickness of this layer was about 3 lm. The concentration of
other multivariate cations did not change substantially from
the bulk values, indicating that the monovalent sodium
(Na+) ions are the primary mobile ions responding to the
poling condition used in this study. Beneath this ‘completely’
Na+-depleted layer, a ‘marginally’ Na+-depleted region
(about 10 lm thick) could be noted.
On the cathode side, the sodium ion concentration showed
a gradient profile [Fig. 3(c)]. The sodium concentration
increased slightly in the subsurface reaching a maximum
Fig. 2. SR-IR spectra of the cathode-side glass surface before and value at 3–4 lm from the surface and then gradually
after cleaning with a cotton tip wet with water. Inset shows an AFM decreased at the surface to a value lower than the bulk con-
image of sodium carbonate (image size = 25 lm 9 25 lm; height full centration. This gradient profile was formed because a non-
scale = 650 nm; poling time = 20 min). blocking electrode was used as the cathode.45 When the glass

Fig. 3. (a), (b), (c): EDX line profiles of cross sections of pristine and poled surfaces. Poling time = 40 min.
1224 Journal of the American Ceramic Society—Luo et al. Vol. 99, No. 4

Fig. 4. Ellipsometric spectra (in Ψ and D) and model fits for (a) pristine, (b) anode-side, and (c) cathode-side surfaces. The poling time was
40 min and the incidence angle of SE analysis was 70°. The lines are least-squares fit results. All un-weighted error functions were below
2 9 103, indicating good agreement between experimental data and the least-squares model fit. (d) Refractive index of bulk glass, pristine
surface layer, and Na+-depleted layer as a function of photon energy. The refractive index of the cathode-side surface was almost identical to the
bulk value.

Fig. 5. Schematics of ellipsometric model for (a) anode (sodium-depleted surface); (b) pristine surface; (c) cathode (sodium-gradient surface).

surface was subjected to the negative electrical potential, The sodium-depleted surface at the anode side showed dis-
Na+ ions in the glass were extracted from the glass surface tinct oscillating fringe patterns [Fig. 4(b)]. The structural
and then reduced to the metallic state by reaction with elec- model for the anode side is schematically shown in Fig. 5(a):
trons supplied from the cathode (as recorded as cathodic cur- (1) semi-infinite bulk glass substrate, (2) 90  2 nm thick
rent in Fig. 1(b). The sodium metal on the glass surface interface layer, (3) 2417  5 nm thick Na+-depleted layer,
further reacted with CO2 from the environment, forming (4) 581  6 nm thick interface layer, (5) 1117  3 nm thick
sodium carbonate particulates (Fig. 2). At the same time, composite of the Na+-depleted layer and 0.85  0.07% void
sodium ions were supplied from the bulk via electrical field- fraction, and (6) 10  1 nm thick bulk glass at the sample/
induced migration. The balance between these two processes air interface. The regression result showed that the total
(sodium ion removal out of the surface and supply from the thickness of the Na+-depleted layer (from 2 to 5) was about
bulk) would determine the final concentration profile of the 4.2 lm, which was in agreement with the EDX measurement
Na+ ion seen in Fig. 3(c). [Fig. 3(b)], and n was 0.01–0.02 lower than the pristine bulk
The thickness and refractive index (n) of the Na+-depleted [Fig. 4(d)].
layer at the anode side and the Na+-gradient layer at the cath- The sodium-gradient within the surface of the cathode side
ode side were analyzed with SE (Figs. 4 and 5). For the did not show any undulating fringes [Fig. 4(c)]. The overall
untreated glass [Fig. 4(a)], the structural model consisted of a refractive index from the model fit was almost identical to
semi-infinite bulk glass substrate as presented in Fig. 5(b): the bulk in the visible wavelength region [Fig. 4(d)]. The fit
261  4 nm thick untreated surface layer covered with result shown in Fig. 4(c) was based on the structural model
46  2 nm thick composite layer of bulk glass and shown in Fig. 5(c) which consisted of a semi-infinite bulk
1.93  0.04% void fraction at the sample/air interface. The ori- glass substrate and a 25  1 nm thick composite layer of
gin of voids at the sample/air interface is attributed to contribu- bulk glass and 94.5  0.2% void fraction. The large void
tions from surface roughness or other subtle differences in the fraction in the model could be interpreted as the roughness
optical response arising from a density deficit or strain in that of this surface. As the Na+ concentration varied gradually
region. The untreated surface layer might be due to the SO2 [Fig. 3(c)], and the average composition of the gradient
dealkalization process during the float glass manufacturing.46 region was very close to the bulk value, the refractive index
April 2016 Structure of Thermally-Poled Glass 1225

(a) (c) (e)

(b) (d) (f)

Fig. 6. Topography (a,c,e) and adhesion force (b,d,f) maps obtained with peak-force tapping AFM imaging of (a,b) pristine, (c,d) anode-side,
and (e,f) cathode-side surfaces. Poling time =10 min. The sampling size is 600 nm 9 600 nm.

The adhesion force measured at 30% relative humidity

condition during the peak-force tapping imaging implied
chemical differences among the three surfaces. The average
adhesion force was 6.8  0.3 nN for the pristine surface
[Fig. 6(b)]. The Na+-depleted surface showed significantly
higher adhesion, 11.1  0.6 nN [Fig. 6(d)]. The Na+-gradi-
ent surface showed a bimodal adhesion force distribution: ~5
nN for the protruded bump region and ~8.6 nN for the
depressed region [Fig. 6(f); in average, 7.2  1.7 nN].

(2) Silicate Network Structure in Thermally Poled

Surfaces
To understand how the electric field-induced migration of
sodium ions altered the silicate network of glass,48 the poled
glass surfaces were analyzed with SR-IR. In SR-IR spectra,
structural information about the Si–O–Si (BO) network can
be deduced from the peak position in the 1060–1120 cm1
Fig. 7. SR-IR spectra of thermally poled soda-lime glass surfaces. region and from the Si–O stretching vibration of NBO or Si–
For comparison purpose, spectra of cathode-side, pristine, and OH groups which appear as a shoulder at ~940 cm1.49
anode-side surfaces as well as fused quartz are stacked with offsets. The SR-IR spectra of the poled surfaces are compared
with those of the pristine surface in Fig. 7. For the Na+-
change was negligible within the resolution of our experiment depleted anode side, the Si–O–Si peak was blue-shifted from
and fit method. 1070 cm1 for the pristine surface to 1096 cm1 (approach-
The surface topography and adhesion force maps of the ing the peak position of pure SiO2, fused quartz, at
pristine, Na+-depleted (anode side), and Na+-gradient (cath- 1122 cm1) as the poling time increased. Note that in the SE
ode side) surfaces are shown in Fig. 6. The prisitine sample analysis, n of the Na+-depleted region decreased toward the
had ring-like features [Fig. 6(a)]. It was speculated that they silica value (1.47). These results implied that the Si–O–Si net-
might originate from the SO2 sodium dealkalization treat- work becomes more “silica-like” as sodium ions migrated
ment used in the commercial float glass process.47 The topo- from the surface into the bulk.50 A small growth of the
graphic images of the Na+-depleted surface were completely shoulder peak at 940 cm1 was also observed as the poling
featureless other than a few random bumps [Fig. 6(c)]. The time increased. This growth cannot be attributed the increase
Na+-gradient surface showed numerous small bumps in the NBO population since Na+ ions were depleted.
[~50 nm wide, ~3 nm tall; Fig. 6(e)]. Note that similar bumps Instead, this growth must be related to an increase in the Si–
were also seen, although less frequently, on the pristine sur- OH groups, which was confirmed by ATR-IR [Section III
face upon the SO2 dealkalization process of the float glass. (3)].4,49 Thus, it can be concluded that the Na+-depletion is
Thus, the topographic features seen in the Na+-gradient sur- accompanied by changes in the silicate glass network struc-
face seem related to the removal of sodium from the surface ture and its terminal sites, most likely converting NBO
(as seen in Fig. 2). The RMS roughness over 600 nm 9 groups to BO and Si–OH groups.
600 nm was 0.3, 0.3, and 1.0 nm for the prisine, Na+- In contrast, the SR-IR spectra of the Na+-gradient cath-
depleted, and Na+-gradient surface, respectively. The signifi- ode side surfaces were almost identical to the pristine sur-
cantly larger roughness for the Na+-gradient surface was face spectrum, regardless of the poling time (Fig. 7). The
also consistent with the SE analysis result [Fig. 5(c)]. only noticeable change was a slight red-shift, for example,
1226 Journal of the American Ceramic Society—Luo et al. Vol. 99, No. 4

Fig. 8. SR-IR spectra of the poled (solid lines) and then reverse-poled (dashed lines) glass surfaces. Both poling and reverse-poling times were
10 min.

Fig. 9. ATR-IR spectra of (a) Na+-depleted and (b) Na+-gradient surfaces of thermally poled soda-lime glass.

~2 cm1 decrease after 20 and 40 min poling. As the ther- (3) Hydrous Species (Si–OH, H2O) in Poled Surfaces
mal poling was carried 200°C (much lower than the glass (A) Analysis with ATR-IR: ATR-IR was employed to
transition temperature), the Si–O–Si network would not monitor the concentration change in hydroxyl groups and
have sufficient thermal energy to fully relax after the field- water molecules in the glass surface. The thickness of the
induced migration of Na+ ions. The local excess or defi- poled layer was on the order of micrometers based on the
ciency of Na+ ions could impose a compressive or tensile EDX and SE analyses. The sampling depth of ATR-IR with
stress to the surrounding Si–O–Si network, which could a Ge crystal is between 1.5 and 3 lm in the 4000–1500 cm1
alter the Si–O–Si bond angle from its initial state.51 There region and the ATR-IR peak intensity is proportional to the
was no discernable change in the shoulder peak intensity at concentration of functional groups within this sampling
940 cm1. depth.40 Thus, ATR-IR is a good technique to assess changes
To test if these structural changes are reversible, re-poling in the amount of hydroxyl and water in the glass.
under a reverse bias was performed. As shown in Fig. 8(a), The ATR-IR spectra of the Na+-depleted and Na+-gradi-
the structure of the initially Na+-depleted surface did not ent surfaces are presented in Fig. 9. While very minimal spec-
change significantly upon applying the reverse poling. This tral changes were observed for the Na+-gradient surface
suggested that the “silica-like” network formation upon the [Fig. 9(b)], the Na+-depleted surface spectra showed the sig-
Na+-depletion is irreversible. The newly formed Si–O–Si nificant growth of the broad peak spanning from 3700 to
(BO) network did not dissociate and return to the original 2600 cm1 with increasing poling time [Fig. 9(a)]. This is
NBO state during the reverse poling at 200°C. direct evidence that the OH concentration in the Na+-
In the case of the Na+-gradient cathode side [Fig. 8(b)], depleted layer is significantly increased, which is consistent
the Si–O–Si peak position was shifted from 1068 to with the growth of the 940 cm1 shoulder peak in SR-IR
1090 cm1 after reverse-poling for 10 min. This result sug- spectra of anode-side surfaces shown in Fig. 7. For a poling
gested that the Na+ ions in the cathode-side surface are still time longer than 20 min, even the bending vibrational mode
highly mobile and readily migrate back to the bulk when a of molecular water at 1640 cm1 was detected. These results
positive bias voltage is applied. As the NBO shoulder peak indicate that proton and water enter into the Na+-depleted
at ~940 cm1 [as well as the OH intensity as shown in Sec- region to compensate the field-induced migration of cations
tion III (3)] did not change in the Na+-gradient surface, the into the bulk. In the cathode side, however, the ingress of
concentration gradient of sodium ions observed EDX water species into the Na+-gradient surface is negligible.
[Fig. 3(c)] does not seem to be accompanied by the restruc- (B) Speciation with SFG: Vibrational SFG spec-
turing of the NBO groups. troscopy is well-known for its ability to detect molecular
April 2016 Structure of Thermally-Poled Glass 1227

species at interfaces.52 In SFG, two photons irradiating the can provide structural information about the subsurface OH
surface are combined and emitted as a single photon whose groups present in the region where EDC is generated due to
frequency is the sum of two input photons.52 When one of the ion concentration gradient.13,26 For a glass surface with
the irradiating photons is in the mid-IR range, then SFG can negligible amount of ions (such as fused silica), EDC is negli-
probe vibrational modes of species at the interface. While gible before thermal poling.13
SHG provides information on the strength of the frozen dc The SFG spectra of the Na+-depleted and Na+-gradient
electric field in the poled layer, SFG provides vibrational are shown in Fig. 10. The insets show the peak deconvolu-
spectroscopic information of chemical species in this frozen tion with Lorentzian functions65 for the surfaces poled for
electric field region.53,54 Note that the interface does not nec- 40 min. A total of five peaks were used for the OH stretch
essarily mean a sharp boundary of two phases, which would region and three peaks for the CH stretch region. The CH
be mathematically described as a step function. If a composi- stretch peaks come from adventitious hydrocarbon species
tional profile of a constituent element varies gradually across adsorbed on the glass surface from airborne organic contam-
this boundary, the entire gradient region can be the interface inants. The small negative doublet peaks near ~2350 cm1
responsible for the SFG response. are an artifact made because the IR power delivered to the
For the poled glass surface, SFG signals (ISFG) can origi- sample is attenuated through the absorption by CO2 in air;
nate from two sources—the noncentrosymmetrically arranged thus, those two peaks were ignored in peak fitting. The same
functional groups and the electric field effects:55,56 peak fitting method was applied to all spectra and the fit
results are summarized in Table S1 in the Supporting Infor-
2 mation.
ISFG / E2xVIS þxIR / ½ðvð2Þ þ vð3Þ EDC ÞExVIS ExIR  (1)
The multiple SFG peaks in the 3000–3700 cm1 region for
the pristine glass surface are consistent with the previously
where xVIS and xIR are the frequencies of visible and IR reported SFG spectra of soda-lime float glass.13 These peaks
photons irradiating to the surface, respectively, and are relatively sharper than typical SFG signals observed for
xVIS + xIR is the frequency of the emitted photon. ExVIS þxIR , the water molecules at the air/liquid interface or adsorbed on
ExVIS , and ExIR are the electric fields of sum-frequency, visi- the fused quartz surface.66,67 The narrow peak width can be
ble, and IR photons, EDC is the electric field produced by interpreted as the lack of long-range hydrogen bonding
the concentration gradient of ions inside the surface, and v(2) interactions.68–70 Thus, they could not be attributed to the
and v(3) are the second-order and third-order nonlinear sus- water layer adsorbed on the glass surface (v(2) responses).
ceptibilities of vibrational modes in resonance with the Instead, the sharp OH peaks could be attributed to the Si–
incoming IR frequency. The v(2) term can have nonzero val- OH groups converted from NBO upon leaching of Na+ and
ues only for the noncentrosymmetrically arranged vibrational neutralization by H+, that is, v(3) EDC responses. Depending
modes. Typically, molecules at the surface are responsible for on the size of the original NBO site, they can have hydro-
the v(2) response.57,58 The molecules in the subsurface region gen-bonding interactions with additional water molecules
(which are responsible responsible for v(3) term) of a bulk absorbed from the gas phase into the glass. Thus, the com-
material with random structures are normally SFG-inactive pensation of the Na+ ions separated from the NBO sites
because v(3) alone does not meet the noncentrosymmetry could be considered to be stoichiometrically equivalent to
requirement. However, if the subsurface is poled and a net either proton or hydrated protons (H3O+, H5O2+, etc.).71,72
EDC is formed, then the v(3) EDC term will be SFG-active Their relative abundance will depend on the size of the origi-
since EDC is noncentrosymmetric.59–63 The orders of magni- nal NBO site and the activity (or concentration) of water in
tude for molecular hyperpolarizability for v(2) and v(3) terms the glass. The SFG peak positions of these species are gov-
are ~1032 cm4V1s1 and ~1039 cm5V2s1.64 Since typical erned by the strength of hydrogen bonding interactions.73–75
EDC of thermally poled surfaces is on the order of ~108 V/ As the hydrogen bonding interaction increases, the redshift
m,26,60 the hyperpolarizability of the v(3) EDC term becomes of the OH peak position becomes larger.75,76 Thus, the small
comparable to that of the v(2) term. Thus, the v(3) EDC term variance in the O–HO distance will result in a larger broad-

Fig. 10. SFG spectra of (a) Na+-depleted and (b) Na+-gradient surfaces of thermally poled soda-lime glass.
1228 Journal of the American Ceramic Society—Luo et al. Vol. 99, No. 4

ening in the peak width for the lower frequency peaks, com- 3500–3570 cm1, compared to other peaks, is higher for the
pared to the higher frequency ones with weaker interactions. Na+-depleted surface (anode side) than the Na+-gradient
An extremely broad peak centered at 2650–2850 cm1 spe- surface (cathode side). This difference might imply that the
cies was detected for the poled surfaces, which was not 3500–3570 cm1 species are the newly formed OH groups by
noticed in the previous report for the pristine soda-lime float the reaction of NBO with H+ or H2O upon the migration of
glass.13 This peak must be the strongly hydrogen-bonded Si– Na+ ions into the bulk.
OH species in the bulk. This component is observed as big Another important observation is that the SFG peaks
as the >3000 cm1 peaks in transmission IR spectra of soda- of the adventitious hydrocarbon contaminants on the sur-
lime glass.77 It is also detected as a minor component in face appeared as positive peaks above the OH peaks in the
ATR-IR spectra [e.g., see Fig. 9(a)]. It appears that the EDC Na+-depleted surface spectra and negative peaks in the
field formed inside the glass upon thermal poling makes this Na+-gradient surface spectra (Fig. 10 inset). This difference
species SFG active. supported that the enhanced SFG signals for the thermally
The weak peak at 3750–3800 cm1 was observed for the poled surfaces are largely due to the v(3) EDC effect. As
pristine glass surface. Its intensity did not grow with thermal shown in eq. (1), the SFG signal is proportional to
poling. This peak could be ascribed to the silanol groups at (v(2) + v(3)EDC)2. Here, the sign of the adsorbed hydrocarbon
the glass surface, although its peak position is slightly higher signal does not change, but the sign of the EDC field changes
than typical values for the free OH group (3700–3740 cm1) depending on the poling direction. Thus, the amplitude of
without hydrogen-bonding interactions with neighboring the total signal depends on the relative phase relation
molecules. The origin of this slight blueshift is not well between these two components.78 The fact that Na+-depleted
understood at this moment. and Na+-gradient surfaces showed hydrocarbon peaks in the
Figure 10 and Table S1 clearly show that four peaks at opposite directions with respect to the OH signal implied
2650–2850 cm1, 3200–3350 cm1, 3500–3570 cm1, and that the EDC fields formed inside the glass surface upon ther-
3650–3700 cm1 are growing with thermal poling. The ATR- mal poling are opposite for the anode and cathode sides.
IR analysis results (Fig. 9) revealed that the concentration of The thermal stability of the Na+-depleted and Na+-gradi-
the OH species increases in the Na+-depleted surface (anode ent layers was tested by annealing the poled glass at 200°C,
side), while that does not change in the Na+-gradient surface the same temperature used for thermal poling, without
(cathode side). Thus, the increase in the SFG signal for the applied electrical bias. At this temperature, sodium ions have
Na+-gradient surface must be mostly due to the v(3) EDC enough mobility, so they can diffuse to reduce the concentra-
effect and the SFG change for the Na+-depleted surface is tion gradient. Figure 11 presents the ATR-IR and SFG spec-
the combination of both OH concentration change and the tra of the poled samples before and after the 200°C heat
v(3) EDC effect. It is noted that the relative intensity of the treatment in ambient air. In the ATR-IR spectra of the

Fig. 11. (a,b) ATR-IR and (c,d) SFG spectra of Na+-depleted (a,c) and Na+-gradient surfaces of thermally poled soda-lime glass before and
after postannealing at 200°C for 2 h in ambient air.
April 2016 Structure of Thermally-Poled Glass 1229

Na+-depleted surface, the 200°C heating caused only a 6

J. G. Wang, M. E. Stahley, C. G. Pantano, D. H. Yang, T. Anderson, and
minor decrease in the OH concentration [Fig. 11(a)]. In other L. Kuhn, “Nanoindentation and Nanowear Studies of Sputter-Deposited
Ultrathin Tin Oxide Films on Glass Substrates,” MRS Proc., 695, 2–7 (2001).
words, 200°C was not high enough to induce dehydration 7
H. A. Schaeffer, M. Stengel, and J. Mecha, “Dealkalization of Glass Sur-
reactions of the OH groups inside the Na+-depleted layer. faces Utilizing HCI gas,” J. Non. Cryst. Solids, 80 [1–3] 400–4 (1986).
8
The SFG intensities showed a much larger decrease after F. Geotti-Bianchini, M. Preo, and C. G. Pantano, “Study of Lubricating
heating at 200°C [Fig. 11(c)]. Two possible reasons can be Coatings for Glass Containers With Optical Microscopy and FTIR Micro-
scopy,” Glas. Technol, 43 [4] 147–56 (2002).
considered—the slight reduction in the OH concentration or 9
J. R. Shallenberger, E. E. Metwalli, C. G. Pantano, F. N. Tuller, and D. F.
the reduction in the EDC field due to repopulation of Na+ Fry, “Adsorption of Polyamides and Polyamide-Silane Mixtures at Glass Sur-
ions via diffusion from the bulk. Although it is difficult to faces,” Surf. Interface Anal., 35 [8] 667–72 (2003).
10
determine which factor is more dominant, one can speculate N. J. Smith and C. G. Pantano, “Leached Layer Formation on Float
Glass Surfaces in the Presence of Acid Interleave Coatings;,” J. Am. Ceram.
that the latter is the case since the relative intensities of dif- Soc., 12, 736–44 (2008).
ferent OH species did not change substantially. 11
E. A. Leed and C. G. Pantano, “Computer Modeling of Water Adsorp-
For the Na+-gradient surface, no additional OH groups tion on Silica and Silicate Glass Fracture Surfaces,” J. Non. Cryst. Solids, 325
were formed during the poling process [Fig. 9(b)]. So, there [1–3] 48–60 (2003).
12
T. A. Guiton and C. G. Pantano, “Infrared Reflectance Spectroscopy of
was no change in the OH intensity in ATR-IR upon heating Porous Silicas,” Coll. Surf. A Physicochem. Eng. Asp, 74 [1] 33–46 (1993).
to 200°C [Fig. 11(b)]. However, the OH SFG intensities 13
L. C. Bradley, et al., “Hydronium Ions in Soda-Lime Silicate Glass Sur-
dropped significantly after heating at 200°C [Fig. 11(d)]. This faces,” J. Am. Ceram. Soc., 96 [2] 458–63 (2013).
14
must be solely due to the repopulation of Na+ ions through M. M. Smedskjaer, J. C. Mauro, and Y. Yue, “Ionic Diffusion and the
Topological Origin of Fragility in Silicate Glasses,” J. Chem. Phys., 131 [24]
diffusion, reducing the EDC field in the surface.60 The struc- 1–10 (2009).
tural distribution of the OH groups in the glass surface did 15
S. Karlsson, B. Jonson, and C. St alhandske, “The Technology of Chemical
not seem to vary since the relative intensities of the OH SFG Glass Strengthening - A Review,” Glas. Technol. Eur. J. Glas. Sci. Technol.
signals did not change. Part A, 51 [2] 41–54 (2010).
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U. K. Krieger and W. A. Lanford, “Field Assisted Transport of Na+ Ions,
Ca2 + Ions and Electrons in Commercial Soda-Lime Glass I: Experimental,”
J. Non. Cryst. Solids, 102 [1–3] 50–61 (1988).
IV. Conclusion 17
J. Zakel, M. Balabajew, and B. Roling, “On the Mechanism of Field-
Through the use of nonblocking electrodes, we studied the Induced Mixed Ionic–Electronic Transport During Electro-Thermal Poling of
a Bioactive Sodium–Calcium Phosphosilicate Glass,” Solid State Ionics, 265,
effects of thermal poling on the surface composition, mor- 1–6 (2014).
phology, and structure of commercial soda-lime silicate float 18
A. Canagasabey, C. Corbari, Z. Zhang, P. G. Kazansky, and M. Ibsen,
glass. On the anode side, a Na+-depletion layer was formed “Broadly Tunable Second-Harmonic Generation in Periodically Poled Silica
within the glass surface. On the cathode side, a Na+-gradient Fibers.,” Opt. Lett., 32 [13] 1863–5 (2007).
19
Y. Quiquempois, G. Martinelli, P. Dutherage, P. Bernage, P. Niay, and
layer was formed. The Na+-depletion was accompanied by M. Douay, “Localization of the Induced Second-Order non-Linearity Within
irreversible restructuring of the silicate network and an Infrasil and Suprasil Thermally Poled Glasses,” Opt. Commun., 176 [4] 479–87
increase in the Si–OH and H2O concentrations. The Na+- (2000).
20
gradient layer on the cathode side did not exhibit substantial A. L. Moura, E. M. Nascimento, M. T. Araujo, M. V. D. Vermelho, and
J. S. Aitchison, “Voltage Thresholdlike Evidence During Thermal-Electric
restructuring of the network nor the uptake of water from Field Induction of Second Order Nonlinearity in Soda-Lime Glasses,” J. Appl.
the environment. SFG analyses of these surfaces showed at Phys., 105 [3] 036106, 3pp (2009).
least three distinct hydrous species (3200–3270 cm1, 3500– 21
N. J. Smith, M. T. Lanagan, and C. G. Pantano, “Thermal Poling of
3550 cm1, and 3650–3700 cm1) in the glass surface, in Alkaline Earth Boroaluminosilicate Glasses With Intrinsically High Dielectric
Breakdown Strength,” J. Appl. Phys., 111 [8] 083519, 9pp (2012).
addition to the strongly hydrogen bonded bulk species 22
B. Ferreira, E. Fargin, J. P. J. Manaud, G. Le Flem, V. Rodriguez, and
(<2800 cm1). The relative abundances of these species were T. Buffeteau, “Second Harmonic Generation Induced by Poling in Borophos-
different for Na+-depletion and Na+-gradient layers. phate Bulk and Thin Film Glasses,” J. Non. Cryst. Solids, 343 [1–3] 121–30
(2004).
23
N. Mukherjee, R. A. Myers, and S. R. J. Brueck, “Dynamics of Second-
Acknowledgments Harmonic Generation in Fused Silica,” J. Opt. Soc. Am. B, 11 [4] 665–9
(1994).
24
This work was supported by the National Science Foundation (grant no. M. Dussauze, et al., “How Does Thermal Poling Affect the Structure of
DMR-1207328). H. He was supported by the Research Exchange program of Soda-Lime Glass?” J. Phys. Chem. C, 114 [29] 12754–9 (2010).
25
the NSF International Materials Institute for New Functionality in Glass T. Cremoux, et al., “Trapped Molecular and Ionic Species in Poled
(grant no. DMR-0844014). The authors acknowledged Asahi Glass Company Borosilicate Glasses: Toward a Rationalized Description of Thermal Poling in
for providing float glass and Dr. Sudarshan Natarajan at Momentive for pro- Glasses,” J. Phys. Chem. C, 118 [7] 3716–23 (2014).
26
viding HOPG for this study. M. Dussauze, et al., “Thermal Poling of Optical Glasses: Mechanisms and
Second-Order Optical Properties,” Int. J. Appl. Glas. Sci, 3 [4] 309–20 (2012).
27
C. Mariappan and B. Roling, “Investigation of Bioglass–Electrode Inter-
Supporting Information faces After Thermal Poling,” Solid State Ionics, 179, 671–7 (2008).
28
E. C. Ziemath, V. D. Ara ujo, and C. a. Escanhoela, “Compositional and
Additional Supporting Information may be found in the Structural Changes at the Anodic Surface of Thermally Poled Soda-Lime
online version of this article: Float Glass,” J. Appl. Phys., 104 [5] 054912, 7pp (2008).
29
H. He, J. Luo, L. Qian, C. G. Pantano, and S. H. Kim, “Thermal Poling
of Soda Lime Silica Glass. Part II. Surface Mechanical Properties Change
Table S1. Position, Width, and Height of OH Stretch Enhanced Mechanochemical Properties of Soda Lime Silica Glass Under Ther-
Peaks Observed in SFG Spectra mal Poling,” J. Am. Ceram. Soc., (2015). doi: 10.1111/jace.14080.
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