Nuclear Magnetic Resonance and FTIR Structural Studies on Borosilicate Glasses Containing Iron Oxide

The structure of borosilicate glasses of composition 30Na2O-2Al2O3-25SiO2-xFe2O3 (43-x) B2O3 has been investigated in the composition range of 0.5 20 mol% Fe2O3. Al, B, 29 Si MAS NMR and FTIR spectroscopies have been used to measure the fraction of different structural species in the glasses. It is evidenced from NMR data that both sodium and Fe2O3 (in low region up to 7 mol%) are the main glass modifier. Structural determination for borosilicate glasses with a high content of (Fe2O3) was carried out by FTIR spectroscopy, where both B and Si MAS NMR are impossible because of the high quantities of paramagnetic iron (III) species present. NMR analysis was performed on borosilicate glasses containing up to 7 mol% Fe2O3 and the N4 values obtained by FTIR spectroscopy agree within error with the B NMR results of the same glass samples. Fe2O3 is a main glass modifier in the low-Fe2O3-content region (≤6 mol%). On other hand, it plays the role of glass former at higher content of Fe2O3. Increasing both N4 of boron tetrahedral units and chemical shift of silicon nuclei to reach maxima at 5 mol% Fe2O3 confirms the role of Fe2O3 as a glass modifier in the low composition region. On the other hand, fast decrease in N4 with further increasing Fe2O3 contents (≥6 mol%) is an evidence for iron oxide to inter the glass network as a network former.


Introduction
Ternary and quaternary borosilicate glasses (BSG) have an extended variety of industrial importance due to their different types of applications.They have been used as sealing components.For example, some of glass compositions have been simply used as sealants in television tubes or bulb lamps.On the other hand, increasing achievements of microelectronics and new demands necessitates new types of glasses.Recent studies have concentrated on borosilicate glasses, which have been developed as sealants, particularly, for molten carbonate fuel cells (MCFC) [1] [2].
Because of the technological advantages, these glasses have long been the subject of structural studies, using different techniques, including 29 Si and 11 B MAS NMR and FTIR spectroscopy [3]- [7] to offer a quantitative analysis of different structural units forming the glass network.The structure of borosilicate glasses is based on Q units, where n is the number of bridging oxygen atoms per tetrahedron, and [BO 3 ] and [BO 4 ] units.The [BO 3 ] units are triangle boron in both ring and non-ring configuration, while [BO 4 ] ones are boron atoms in tetrahedral coordination.The oxygen atoms can be bonded to one boron and three silicons (1B, 3Si) or four silicon atoms (0B, 4Si) and have a Na + ion as a charge compensator.
The distribution of the borate and silicate structural units depends on two structural factors namely R and K. Generally, R is the ratios of Na 2 O/B 2 O 3 and K is the ratio of SiO 2 /B 2 O 3 [8] [9].Dell et al. [8] proposed a structural model for which the variation of [BO 4 ] borate units (N 4 ) is represented as a function of the R parameter.For all K values, N 4 increases up to a maximum in between 0.5 and 0.75 for R = 1, and the value of this maximum increases with an increasing K values.Then, the proportion of N 4 slowly decreases for higher R values.
In present study, two individual composition regions of borosilicate glasses were investigated in order to test the possible quantitative use of NMR and FTIR spectroscopy.
The first type contains a limited concentration from Fe 2 O 3 as a paramagnetic material.
In such a case NMR study can easily be applied to obtain values of Q n and N 4 fraction in the borosilicate glass.On the other hand, the second type of borosilicate glasses contains further high level from Fe 2 O 3 (>6 mol%).These concentrations are unsuitable for NMR measurements.This is because the variation in local fields due to the unpaired electron spins produces sufficient broadening of NMR lines [10].As a result, different contributions cannot be resolved and some may even be unobservable.FTIR spectroscopy is not affected by the presence of paramagnetic species and therefore it would be a very useful tool for quantitative measurement of structural fractions, such as Q n in silicate and N 4 in borate networks where NMR is impracticable.In this study, FTIR spectroscopy can be applied for all glass compositions while MAS NMR technique is applied only on glasses of low Fe 2 O 3 concentration (≤6 mol%).

Sample Preparation
The modified borosilicate glasses were prepared by melting batches in alumina crucibles at a temperature ranging from 1250˚C to 1520˚C depending on composition.
Then the melt was quenching over a stainless steel plate.The batches were prepared from reagent grade SiO 2 , H 3 BO 3 , Na 2 CO 3 , Al 2 O 3 and Fe 2 O 3 .

Nuclear Magnetic Resonance
All samples were measured with JEOL GSX-500 high-resolution solid-state MAS NMR spectrometer in a magnetic field of 11.4 T. 29 Si MAS NMR spectra were recorded at a frequency of 99.3 MHz and a spinning rate of 6 kHz.A cylindrical zirconia sample holder was rotated at a speed depends on the type of the measured nuclei.The applied pulse length was 2.62 µs and a recycle delay of 30 s. typically 1000 -2000 scans were acquired. 11B MAS NMR spectra were recorded at a frequency of 160.4 MHz and spinning rate of 15 KHz.The glass samples were measured with a single pulse length of 0.5 -1.0 ms and a pulse delay of 2.5 s, and an accumulation of 100 -200 scans. 27Al MAS NMR spectra were recorded at a frequency of 130.3 MHz and spinning rate of 6 KHz.

FTIR Measurements
Fourier transform infrared absorption signals of the studied glasses were measured at room temperature (20˚C) in the wavelength range 4000 -400 cm -1 using a computerized recording FTIR spectrometer (Mattson 5000, USA).Fine powdered samples were mixed with KBr in the ratio 1:100 for quantitative analysis and the weighed mixtures were subjected to a load of 5 t/cm 2 in an evocable i.e. to produce clear homogenous discs.Then, the IR absorption spectra were immediately measured after preparing the discs to avoid moisture attack.

Results and Discussion
There is a wide range of compositions which can form glass in the silicate and borosilicate systems [3]  rimental results are mostly obtained on modified borosilicate glasses having R > K in all cases, since R changes between 0.7 and 1 and K changes from 0.58 to 0.67.In this case, the modifier oxide is participated between both the borate and the silicate network.

Iron Free Borosilicate Glass
It was known that Al 2 O 3 plays the role of both glass former and modifier in the network of the glass [15] [16].This depends upon the type of the glass and the content of Al 2 O 3 .
In our case, the Al 2 O 3 inters the glass as a network former, since the value of chemical shift of the Al spectrum Figure 1 is 59.6 ppm which assures that the aluminum is found in tetrahedral coordination which means that Al 2 O 3 is consumed as a glass former.

FTIR Spectroscopic Analysis
Figure 7 shows FTIR spectra obtained for the studied sodium borosilicate glasses containing different concentrations from Fe 2 O 3 .It can be realized from this figure that there are well defined FTIR envelops appeared at about 800 and 1580 cm −1 in glasses containing up to 6 mol% Fe 2 O 3 concentrations.The FTIR envelop cited at about 800 cm -1 is assigned to NBO atoms in Q 2 and Q 1 species.This envelop is totally disappeared and the new IR peak at about 1285 cm −1 is clearly seen at higher Fe 2 O 3 concentrations.
The well-defined envelops at 800 cm −1 and 1580 cm −1 are assigned to vibration of Si-O (non-bridging bonds) in different silicate networks [11] [13] [17] as a result of addition of Fe 2 O 3 (up to 6 mol%).Disappearing of these envelops and appearance of new one at 1285 cm -1 leads that concentration of NBO in the silicate network is reduced upon more addition of Fe 2 O 3 (≥6 mol%).The appearance of the envelop at about 1285 cm −1 is assigned to stretching vibration of Fe-O in iron silicate and borate species, as a glass forming groups [18]- [21].On other wards, Fe 2 O 3 in such situation plays, as suggested above, the role of glass former.It can remove NBO from the silicate network and as a result it consumes part of the modifier to form FeO 4 groups.In such situation, Si-O-Fe bonds are constructed and it played the role of shielding silicate units.
Quantitavely, Figure 8 presents change of the fitted areas representing NBO and concentration of FeO 4 as a glass former against Fe 2 O 3 content.The relative area of the peak centered at about 800 cm −1 is clearly seen to increase with increasing Fe 2 O 3 content, see Figure 8 (between 0 and 5 mol%).On the other hand, at higher Fe 2 O 3 content the envelope at 800 cm −1 is decreased and vanished and other envelop at 1280 cm −1 is rather appeared.The increasing behavior of relative area (at 800 cm −1 ) may indicate an increase of the number of non-bridging oxygen atoms upon addition of Fe 2 O 3 in silicate network.Higher area means higher concentration of modifier in the silicate network upon addition of 6 mol% Fe 2 O 3 .In this case we suggest that most of Fe 2 O 3 enter the borosilicate network as an effective modifier.The relative area of the envelope at 1280 cm −1 (see Figure 8) is remarked to increase upon addition of more Fe 2 O 3 (>5 mol%).These features are suggested to be due to reducing the content of modifier and NBO in the network of the glasses due to changing the structure role of iron from modifier to former.Presence of the well resolved envelope at about 1280 cm −1 confirms the presence of iron as a former units connected to BO 3 groups as basic former units.Presence of Fe 2 O 3 as a glass former should in turns reduce the fraction of boron tetrahedral units and NBO in the silicate network.

Conclusion
Borosilicate glasses containing different concentrations from Fe 2 O 3 have been prepared and investigated with FTIR and NMR spectroscopy.At low concentration from Fe 2 O 3 (≤6 mol%), iron oxide inters the glass network as a modifier.On the other hand, Fe 2 O 3 is consumed as a glass former at higher concentration.The modifier part of iron oxide is consumed to form NBO in silicate and bridging bond in borate network.As a result Q 2 was found as the main units in silicate network.The fraction of boron tetrahedral N 4 was found to increase in glasses of up to 6 mol% iron oxide.At higher concentration N 4 decreases due to the action of Fe 2 O 3 as a glass former.

Figure 2
Figure 2 presents 29 Si NMR spectrum of iron free borosilicate glass.The chemical shift () of base glass is appeared at −88.4 ppm which is related to Q 2 species.This leads that the modifier oxide is consumed to break two bridging bonds as an average per each tetrahedral SiO 4 unit.Figure 3 shows experimental 29 Si MAS NMR for glasses containing different concentrations from Fe 2 O 3 (0, 5 mol%).Comparing the two spectra, it can be seen from this figure that there is remarkable shift in the peak position between the spectral lines of 29 Si NMR of iron free glass and one contains 5 mol%

Figure 2 .
Figure 2. 29 Si NMR spectrum of iron free glass.

Fe 2 O 3 .
The substitution of 5 mol% B 2 O 3 by 5 mol% Fe 2 O 3 has a clear effect on the chemical sifts () of silicon nuclei.() of base glass is appeared at −88.4 ppm, but the chemical shift value () of glass containing 5 mol% is increased to reach −84.4 ppm upon addition of 5 mol% Fe 2 O 3 .This means that most of all of Fe 2 O 3 is consumed as suggested above as a modifier, which results in increasing the concentration of NBO in silicate network.Increasing NBO atoms in silicate network is reflected from increasing behavior of chemical shift with increasing Fe 2 O 3 content Figure 4.This confirms that silicate units are deshielded or depolymerized with increasing iron oxide content in the region up to 6 mol%.

Figure 3 .
Figure 3.Chemical shift of 29 Si NMR spectra of iron free (at bottom) and for glass contains 5 mol% iron oxide.

Figure 5
Figure 5 shows experimental 11 B MAS NMR for glasses containing different concentrations from Fe 2 O 3 .spectrum at the bottom was obtained from sodium borosilicate glass (free from Fe 2 O 3 ) with R = 0.7 and K = 0.58.The second two spectra were obtained from a glass containing 3 and 5 mol% Fe 2 O 3 with R around 0.9.It can be seen from this figure that there is no remarkable shift in the peak position of the spectral lines of 11 B NMR. Substitution of 5 mol% B 2 O 3 by 5 mol% Fe 2 O 3 has no effect on the chemical shifts () of boron nuclei.Chemical shift of BO 4 is appeared at 0 ppm for all investigated samples.But the fraction of boron tetrahedral units (N 4 ) is only affected, since it changed from 0.52 to 0.65 upon addition of 5 mol% Fe 2 O 3 , see Figure 6.This means that substitution of B 2 O 3 by Fe 2 O 3 results in increasing the concentration of bridging bonds in the borate network through transformation of BO 3 triangle units to BO 4 groups.Fe 2 O 3 is therefore played the role of glass modifier in the region between 0 and 5 mol%.This based on the difference between the values of N 4 for sample free from Fe 2 O 3 and the other containing 5 mol%, since glasses containing Fe 2 O 3 showed higher values of N 4 compared with that of iron free glass, see Figure6.Higher concentrations of Fe 2 O 3 (8 -20 mol%) are unsuitable for both11 B and 29 Si NMR measurements[10].This is because the high level of paramagnetic oxides which can induce local fields due to the unpaired electron spins which in turns produces sufficient broadening of NMR lines.Therefore, structure of glasses in the higher composition region has to be investigated by FTIR absorbance spectroscopy.

Figure 4 .
Figure 4.Chemical shift of 29 Si NMR spectra as a function of Fe 2 O 3 contents.

Figure 5 .
Figure 5. 11 B NMR spectra of selected composition of modified borosilicate glasses containing Fe 2 O 3 .

Figure 6 .
Figure 6.Fraction of boron tetrahedral as a function of Fe 2 O 3 concentration.

Figure 8 .
Figure 8. Changes of relative area of both IR peaks centered at 800 cm −1 and