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Measurement of Trace Silanol in Siloxanes by IR Spectroscopy

E L M E R D. L I P P
Analytical Research Department, C041C1, Dow Corning Corporation, Midland, Michigan 48686-0994

Two novel approaches for the measurement of trace SiOH moieties in siloxane polymers by IR spectroscopy are described. Both methods are based on the idea of selective spectral modification of SiOH absorbance bands so that the silanol absorbance bands can be isolated in the presence of much larger, overlapping background absorbances. Modification of the SiOH groups is made to occur either through H-bonding using mixed solvent systems or through deuteration resulting from isotope exchange in the presence of excess D20. Both techniques have high specificity for SiOH groups over other portions of the molecules and produce only minimal changes in the IR absorbances due to non-silanol moieties. Subtraction of a modified sample spectrum from an unmodified spectrum then allows the SiOH absorbances to be isolated and quantitatively measured to low concentrations. These techniques allow one to circumvent a major limitation of IR spectroscopy for trace analysis, namely, the need to rely on a separate reference material for the removal of interfering background absorbances. Of the two methods described in this paper, the deuteration approach is superior in terms of ease and sensitivity. Measurements can be made down to 10 ppm (wt OH/wt sample), which is close to the noise level of the spectral measurement. Index Headings: Infrared spectroscopy; Polydimethylsiloxane; Hydrogen bonding; Deuteration; Trace OH; Silanol.

silanol in polydimethylsiloxane (PDMS) and related polymers. These approaches use two properties of the silanol moiety, namely, the ability to form H-bonds and rapid hydrogen-deuterium exchange, to allow isolation of the silanol absorbances and permit their measurement at trace levels. In both cases it is the ability to modify the silanol moieties without significantly affecting the rest of the molecule which leads to success. Both IR approaches offer sensitivity comparable to that of the chemical techniques, along with better specificity and ease. Of the two IR approaches, deuterium exchange is found to be superior and is discussed in greater detail. In a broader sense, the selective modification of spectral absorbances discussed here provides an elegant example of how high-quality IR spectra of trace constituents can be obtained from a single material without reliance on a separate reference material. EXPERIMENTAL All of the measurements were performed on a Nicolet 60SX FT-IR with standard mid-IR optics and data collection parameters for 8 cm -1 resolution (2048 data points, 4096 transform points with the use of every other zerocrossing of the HeNe laser). MCT and PbSe detectors were used interchangeably in this work. An optical filter which removed light frequencies below 2300 cm -1 was placed just prior to the sample for all measurements. The data were collected in block format with the use of a moveable sample mount under computer control. Data collection alternated between the sample and a clear beam background. Five blocks of single-beam background spectra were interspersed with four blocks of single-beam sample spectra. Each sample spectrum was then ratioed against the clear beam backgrounds collected immediately before and after, and the ratioed spectra were averaged to get a final sample spectrum. There were 64 scans in each block (256 sample scans total) and the total time for data collection and processing was 5 min. This type of block averaging compensates for small instrumental or atmospheric fluctuations with time and is very helpful when IR spectroscopy is being used for trace analysis. It is especially important in this work to have all traces of atmospheric water absent from the spectra since its OH stretches overlap the spectral region of interest. The solvents used in this study (CC14, 1,4-dioxane, THF) were dried over 4A molecular sieves at least overnight, prior to use. The siloxanes were standard materials obtained within Dow Corning and have no special characteristics. Quantitation of all results was obtained from calibration curves which were constructed by applying each method to dilute solutions of (HOMe2Si)20 in CC14.

INTRODUCTION Silanol groups (~SiOH) are very important moieties in organosilicon chemistry due to their ease of reactivity. The final properties of many materials are determined by condensation or hydrolysis reactions (both desirable and undesirable) undergone through silanol linkages, and trace silanol impurities can have large effects on the potential applications of these materials. The quantitation of silanol groups, particularly at trace levels, is thus necessary for an accurate prediction of the suitability of a material for a particular application. During the past few decades many analytical approaches to the measurement of silanol groups in siloxanes have been developed. A number of these are discussed in the book edited by Smith. 1 Most of these methods have been chemical in nature and have relied to some extent on the slightly acidic nature of the silanol group. These methods have ultimately been found to be cumbersome, reagent- and time-consuming, and nonspecific for silanol, thus making them susceptible to many impurities. IR measurements 2 have found some application at higher silanol levels, as has N M R ) but neither method is readily applicable to trace (< 1000 ppm) measurements. Despite their known drawbacks, the chemical methods are currently in wide use since they do have sufficient sensitivity for trace determinations. In this paper I wish to describe two new approaches which use IR spectroscopy for the measurement of trace
Received 20 S e p t e m b e r 1990; revision received 19 October 1990.

Volume 45, Number 3, 1 9 9 1


1991Society for Applied Spectroscopy

Past experience with this material at Dow Corning and elsewhere 2 has shown it to be a good calibration standard for PDMS since it is stable and readily synthesized, 4 and the absorptivity of the OH stretching vibration is within a few percent of that seen in silanols on PDMS. The calibration curves generated for each method were linear and passed close to the origin. For siloxanes with other functional groups present, this material is not as appropriate, and absolute errors in quantitation as large as 25% may be experienced. Better calibration standards would certainly improve the quantitative accuracy of the results for these materials, but such standards are often not readily obtained. All measurements in this study were performed at pathlengths of 0.5 or 1 cm for the H-bonding method and 1 cm for the deuteration method with cuvettes having fused-silica windows. The cuvettes also had fitted Teflon @ stoppers to facilitate mixing in the cell and to prevent evaporation. Siloxane concentrations for both studies were about 2.5% (0.125 g siloxane/5 mL). For the H-bonding method, measurements were made on CC14, the H-bonding agent in CC14, the siloxane dissolved in CC14, and a separate portion of the siloxane dissolved in a H-bonding agent/CC14 solution. The concentration of the H-bonding agent was generally 5 or 10%. Once all the spectra were measured, the following iterative spectral subtractions were performed: siloxane/ e e l 4 minus C C l 4 (spectrum A); siloxane/H-bonding agent/ CC14 minus H-bonding agent/CC14 (spectrum B); A minus B (spectrum C). At this point spectrum C contains only those features affected by the H-bonding agent. Reference spectra of H20 in CC14 and H20 in H-bonding agent/CC14 now need to be subtracted. These could be measured only once and then stored on disk for future use, although it is important that the concentration of H-bonding agent in CC14 be kept constant; otherwise, the spectrum of H20 will change and not be subtracted cleanly in the final spectra. Each of these water spectra is subtracted from spectrum C to give the final isolated silanol features. Quantitative measurements were made by measuring the distance from the top of the free OH peak to the bottom of the H-bonded OH peak. If the water spectra have been measured in advance, approximately one hour is required for a silanol determination. The deuteration method requires measurement of the siloxane/CC14 and siloxane/D20/CC14. The steps in this procedure are as follows: (1) measure the siloxane/CCl4 spectrum (spectrum A); (2) add about 0.5 mL D20 directly to the IR cell; (3) shake vigorously for 20 s; (4) allow the D20 to phase separate from the CC14; (5) remove D20 and replace it with a fresh aliquot; (6) repeat the shaking and phase separation; (7) measure the siloxane/ D20/CC14 spectrum (spectrum B). The second aliquot of D20 is left in the IR cell, and care should be taken to ensure that it remains above the IR beam. The difference of A minus B is obtained (spectrum C). Although iterative, the subtraction factor should be very close to 1.00 since the same siloxane sample is used for both measurements. A spectrum of H20 in CC14 (measured once and then stored on disk) is then subtracted iteratively from C to obtain the isolated SiOH features. A spectrum of D20 in CC14 could be subtracted at this point to obtain the isolated SiOD features, but this is not generally done
478 Volume 45, Number 3, 1991

because the OD region is less precise to use for quantitation due to the high D20 concentration following deuteration. The peak height of the OH band is used exclusively for quantitation. D20 subtraction is performed for very low silanol levels, however, since this can improve the appearance of the baseline in the OH region. It generally requires 20 to 30 min to complete a silanol determination. RESULTS AND DISCUSSION Silanol groups in PDMS and related materials have two fundamental vibrational modes associated with them,' these being the OH stretch near 3690 cm -1 (when not H-bonded) and an SiO stretch near 940 cm -1. Of these, the OH stretch is generally the more useful. This absorbance is stronger than the SiO stretch and the SiO stretch is broad and often obscured by the intense SiOSi stretching vibrations between 1100 and 1000 cm -1. In this work only the OH stretching vibration is studied. The silanol groups in siloxane polymers generally occupy terminal positions only, and this is assumed to be the case in this work, also. Any attempt to measure silanol in P D M S by IR spectroscopy must overcome three problems. The first two of these are spectral interference from water and H-bonding. Both of these problems are readily handled by using dilute solutions of the P D M S in CC14 .2 Water is a problem because the OH stretches from it spectrally overlap the silanol OH stretch. In neat samples this overlap is very severe, but for samples dissolved in CC14 the OH stretches of water are sufficiently resolved from that of silanol to allow them to be easily removed by spectral subtraction. 2 Sources of water in these measurements are the siloxane sample and the CC14 solvent, with the latter generally being the predominant source. H-bonding is a problem when a mixture of forms is present, since this produces a complicated spectral contour and one which varies with the concentration of H-bonding species. It is desirable to have only one form of the silanol species present, since this will generally produce only one OH stretching absorbance. Dilution in a nonpolar solvent such as CCl 4 can reduce intermolecular H-bonding between silanols to a negligible level, and the unassociated molecules will exhibit a free OH stretching absorbance which is easily measured and is useful for quantitation. 2 There is some residual intramolecular H-bonding which remains, however, between silanols and oxygens on the SiOSi backbone, 5 and this is unaffected by dilution. This produces a small, broad feature 2 near 3580 cm -1 for siloxanes dissolved in CC14. For the remainder of this work it is assumed that the fraction of molecules participating in this type of intramolecular H-bonding is small and constant for a given material and can be ignored in quantitative applications. The third problem, and the most difficult one, is separation of the silanol absorbance from underlying background absorbances due to the polymer. The spectrum of a typical P D M S in the region of interest is shown in Fig. la. At this level of presentation the silanol absorbance is not identifiable even though the silanol concentration of this material is relatively high, about 500 ppm. The bulk of the absorbance in this region consists of a

U3 I.iJ I.D U Z G: O~ G:


36oo 3~oo

3 6 o o 3 ~ o o 3 4 0 o 3 9 o o 3200

FIG. 1. Spectrashownare (a) PDMS dissolvedin CC14,(b) PDMS in 10% 1,4-dioxanein CC14,and (c) the differencespectrum a - b. Spectral features due to water have alreadybeen removedfrom c. series of combination bands originating from the CH stretches near 2900 cm -1 and the SiC stretches and SiMe rocking modes ~ near 800 cm -1. Near 3700 cm -~, where the silanol absorbance is expected, there actually exist a methyl combination band, water, and silanol, all severely overlapped. The simplest approach at isolating the silanol absorbance is spectral subtraction using another reference material having no (or as little as possible) silanol. Although useful for high silanol levels, this approach is not feasible for low silanol levels (10 to 1000 ppm, typical of PDMS) since silanol-free reference materials are neither readily available nor easily made. Furthermore, the background caused by the siloxane chain varies in appearance with structural changes in the polymer, even for subtle changes such as chain length. A single silanol-free reference material would not be applicable to more than a very narrow range of materials. Efforts at isolating the silanol absorbance through resolution enhancement techniques such as spectral derivatives and Fourier self-deconvolution were also attempted as part of this work, but proved unsuccessful. As an alternative approach, the idea of using a silanolmodified reference, rather than a silanol-free reference, was pursued. The goal of this approach was to modify the silanol moieties in a material in a manner such that the silanol absorbances would be altered but the absorbances from the rest of the molecule would not. Spectral subtraction would then allow isolation of the silanol

absorbance. Two properties of the silanol moiety were exploited in order to effect such a modification: H-bonding, and deuteration through isotope exchange. The basis for regarding each of these approaches as being possibly successful is the fact that an OH stretching vibration, in general, is relatively isolated from the rest of a molecule. That is, for a mode described as an OH stretch, there is very little atomic motion occurring in any of the other atoms in the molecule. This is even more true for OH groups attached to Si than to C since the relatively large size of the Si atom provides vibrational insulation from the remainder of the molecule. 1The completeness of this insulation and, hence, lack of change in background spectral absorbances following sample modification will determine the degree to which these approaches succeed. The details for both the H-bonding and deuteration approaches for measuring trace silanol levels are described below. Both approaches proved successful; the deuteration approach was superior, however, and more space will be devoted to it. The H-bonding approach is still useful and may find application in other problems. H-Bonding Approach. H-bonding is observed in IR spectra as a shift in the OH stretching bands to lower cm -1 along with a broadening of the bands. For COH species, this shift is often on the order of 10 % of the free stretching absorbance, and the exact value depends on the strength of the H-bond along with any steric considerations. Generally, SiOH species are slightly more acidic than COH, and the SiOH species will show a slightly larger propensity to form H-bonds. Overall, the magnitude of the band shifts and broadening expected with SiOH should be comparable to those seen in COH, and this was observed to be the case in studies of SiOHcontaining molecules dissolved in H-bonding solvents. 6 The key to using IR spectroscopy for the measurement of SiOH species at trace levels is to record spectra of the material in two molecular environments which are similar, but differ in that H-bonding can occur in one environment but not the other. If the environments are indeed similar (except for H-bonding), then spectral subtraction can be used to remove those absorbances which are not affected by H-bonding and thus allow the SiOH absorbances to be isolated. The approach to be pursued involves use of a nonpolar solvent in one case (such as CC14), which allows measurement of free SiOH moieties, followed by use of a mixed solvent system for the other, where a small amount of a H-bonding solvent is added to the CC14. In each case the dominant solvent present is CC14, and solvent effects in the IR spectra associated with interactions between CC14 and the nonsilanol portions of the molecule should be the same. The small amount of H-bonding agent added to the CC14 will act as a scavenger in the solution by seeking SiOH moieties and associating with them through H-bonds. If the OH stretching modes are indeed isolated from the rest of the molecule, then these vibrations will be the only ones affected by the presence of the H-bonding agent. An example of this approach is shown in the first figure. Figure la is a spectrum of PDMS dissolved in CC14. Figure lb is a spectrum of the same material dissolved in 10% 1,4-dioxane in CC14 (v/v) with the spectral features associated with the dioxane already removed by spectral subtraction. Comparison of these two spectra shows t h a t

the presence of dioxane causes a loss of intensity in the 3700-cm -1 region and formation of a broad band near 3400 cm -1. Both of these results are consistent with H-bond formation due to the presence of the dioxane. Figure lc shows the isolated SiOH absorbance obtained as the difference spectrum of the CC14 solution minus the dioxane/CC14 solution. Spectral absorbances due to water have already been removed. The order of subtraction causes the free OH bands to point in the positive direction and the H-bonded bands to point in the negative. An important feature of this difference spectrum, in addition to the isolation of the SiOH absorbances, is the flat, featureless baseline on which the silanol absorbances sit. This flat baseline verifies that the background CH absorbances from the siloxane are unaffected by the presence of a small amount of dioxane in the one solution, and these features are thus removed quite efficiently. The results shown in Fig. 1 illustrate some of the important properties of a suitable H-bonding agent for this work. The H-bonding agent must be aprotic since any additional OH or N H added to the system will exhibit unacceptably large absorbances in the spectral region of interest. Other spectral interference could come from C=O and from high CH levels relative to the H-bonding portions, and these moieties should be minimized. The H-bonding agent must be capable of forming strong H-bonds, and compatible with CC14 and siloxanes. Some good H-bonding agents identified for this work, in addition to 1,4-dioxane, are tetrahydrofuran (THF) and diethyl ether. Of these, T H F had the best combination of H-bonding efficiency, low background absorbance, low volatility, and compatibility with siloxanes, and it was the material used for subsequent studies. Other H-bonding materials which gave acceptable results--though not as good overall as the ethers--include trioxane, dimethylsulfoxide, tripropylamine, and pyridine. The latter three gave problems because they were apparently too hygroscopic. The agent 1,3,5-trichlorotriazine was tried, but it did not form H-bonds with the silanol. The exact concentration of the H-bonding agent used in these measurements is also of importance. There are two reasons for this: the H-bonding agent concentration affects the fraction of silanols which get H-bonded, and it also affects the spectral contour exhibited by water. A good value to use with T H F turned out to be 5 %. This caused about 70 % of the SiOH groups to form H-bonds [based on measurements with (HOMe2Si)20], and the spectral interference from this amount of T H F was not severe and could be readily accounted for through spectral subtraction. A consistent value of T H F was always used in a given study so that the spectrum of water was reproducible and could be subtracted. The utility of this H-bonding approach for measuring silanol content in siloxanes is shown in Fig. 2. As was mentioned earlier, the underlying CH background on which the silanol absorbance sits varies slightly with the composition of the siloxane. A seemingly subtle effect, such as chain length (and hence the number of Me3SiOends present), produces variations in the spectral patterns which are as large as the silanol absorbances of interest. In Fig. 2a the attempts at isolating the silanol absorbances through simple spectral subtraction are 480 Volume 45, Number 3, 1991

35 CS

4000 3800 3600 WAVENUMBER 3400 4000 3700 3400 WAVENUMBER 3100

FIG. 2. (a) Difference spectra from the use of a low-silanol 12,000-cS reference material for three different viscosity samples. (b) Isolated silanol features for the same samples with the use of the H-bonding approach.

shown. The reference material in this case is a low-silanol PDMS having a viscosity of 12,000 centi-Stokes (cS). Iterative spectral subtractions with 1000-, 350-, and 35cS materials show results which are useable, though not optimum, for the 1000-cS, poor for the 350-cS, and useless for the 35-cS sample. Other changes in structure, such as cyclic rather than linear structures or the presence of other functional groups, would show even larger discrepancies, and the 12,000-cS reference material would be completely inapplicable to these cases. Measurements on these same materials with the use of the H-bonding approach are shown in Fig. 2b. In each of these cases the isolated silanol absorbances are readily obtained, and a quantitative measure of the silanol levels gave 550 ppm for 1000 cS, 310 ppm for 350 cS, and 110 ppm for 35 cS. The corresponding values from a chemical measurement 7 are 500, 310, and 100 ppm, respectively. The agreement between the two methods is reasonably good. Replicate IR measurements on these samples gave a relative precision of about 10%, and the detection limit for this measurement is in the 20-50 ppm range. At these lower silanol levels, variations in the CH background caused by the presence of the H-bonding agent (a solvent effect) become observable, and the 20-50 ppm detection limit is determined by these variations rather than the noise level of the measurement. Spectral subtraction with a low-silanol reference material, as illustrated in Fig. 2a, may produce artifacts caused by differences in impurities between the sample and reference materials. The H-bonding approach has the advantage that only H-bonding impurities will affect the measurement. Other impurities will not show spectral changes with the H-bonding agent present, and any absorbances from them will be removed by spectral subtraction along with the invariant part of the siloxane

background. Among H-bonding impurities, water is present in both the siloxane and the solvents used for this analysis. The solvents are dried over molecular sieves prior to use, but there remains residual water which can be readily measured. The effects of water must be subtracted from both the CC14 and CC1JTHF solutions, and this has already been done for the spectra shown in Fig. 2b. One problem in this method is subjectiveness in the spectral subtractions involving water. Although the spectrum of water in CC14is well defined and readily removed, the spectrum of water in CC14 with a H-bonding agent is significantly more difficult to subtract. The spectral contour exhibited by water changes markedly with the H-bonding agent concentration, and the presence of the H-bonding agent increases the spectral overlap between SiOH and water, thus making it more difficult to distinguish the two types of OH. It is these difficulties, combined with a simpler experimental procedure for deuteration, which make the deuteration approach described below preferable in most trace silanol measurements. Deuteration Approach. Replacement of H with D on a silanol group shifts the frequency of the hydroxyl stretching vibration from the 3700-cm -~ region down to about 2700 cm-L This is very close to the 2 '~ shift in frequency expected for a doubling in mass of a simple one-dimensional harmonic oscillator and illustrates how the OH species is vibrationally isolated from the rest of the molecule. To develop a method using IR spectroscopy and deuteration for trace silanol measurements, one uses considerations similar to those of the H-bonding approach. The key requirement is that a spectrum of the fully protonated species be measured in a particular environment, and then measured as the deuterated form in the identical environment. If deuteration of the silanol groups does not perturb the rest of the siloxane molecule, then any background absorbances should remain invariant to deuteration and they should be easily removed by spectral subtraction. A viable method has been developed with the use of a dilute solution of the siloxane in CC14 at relatively long pathlength (1 cm). An IR spectrum of the siloxane in this environment is first measured and corresponds to the fully protonated form. Deuteration is then achieved through addition of excess D20 directly to the IR cell. Shaking of the solution produces instantaneous exchange between labile H and D, and the large excess of D (about 1000:1 in most cases) ensures that the siloxane becomes fully deuterated. Due to the immiscibility of water in e e l 4 and the high density of CCI4, the D20 added to the IR cell in this procedure readily phase separates from the CC14 following shaking. Siloxanes, having little solubility in water even when hydroxylated (see Fig. 4, for example) remain in the CC14but are now fully deuterated at the hydroxyl positions. Thus, the spectrum of the deuterated siloxane can now be readily measured in the CC14 phase, and a difference between the original protonated spectrum and the deuterated one allows isolation of the silanol absorbances. The completeness of this isolation depends on the extent to which the siloxane backbone remains unaffected by deuteration. An illustration of this method is shown in Fig. 3. A spectrum of PDMS with a relatively high silanol content

expanded x 3



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s~oo S l O O z~oo 200 NRVENUMBER FIG. 3. These spectra illustrate the deuteration technique. (a) PDMS with high silanol content, about 500 ppm, dissolvedin CCI~.(b) Same sample as a but followingdeuteration. (c) Differenceof a - b showing the isolated silanol features. H~Oand D20 have been removedby spectral subtraction.
is shown in Fig. 3a. Figure 3b shows the spectrum of the sample following deuteration as described above. It is apparent that there has been a loss of intensity in the 3700-cm -1 region and an increase in the 2700-cm -1 region following deuteration, as expected. Spectral subtraction of these two spectra (protonated minus deuterated) isolates the exchangeable H in the system, normally silanol and water. The presence of H20 in the 3700-cm -1 region and D~O in the 2700-cm -~ region can then be removed by spectral subtraction to give the isolated SiOH and SiOD absorbances shown in Fig. 3c. The order of subtraction is such that the SiOH features point in the positive direction while the SiOD features point in the negative. An important feature of Fig. 3c is that the baseline on which the silanol features ride is flat. This proves that the background CH absorbances are unaffected by deuteration since they can be so completely removed by spectral subtraction. Compared to the H-bonding method for trace silanol measurements, the deuteration approach is superior in the following respects: deuteration of the silanol groups is virtually 100% efficient; the detection limit is lower; and fewer spectral subtractions are involved, and they




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o u0


~o co (E o to q2N 0

, sgoo









FIG. 4. The spectrum of (a) a very high silanol material before deuteration is shown, and then following (b) one, (c) two, and (d) three

s~oo s6oo

applications of D20. Spectrumd has been displaced slightlyfromc for clarity. are less subjective. Each of these features is discussed below. The efficiency of deuteration can be determined by applying the technique to a sample of very high silanol content. This was done by using a mixture of PDMS diol oligomers where both ends are OH endblocked, and whose average chain length was 12 siloxane units. The OH concentration in the neat material was measured to be 3.75 % (wt OH/wt sample), which is about 100 times more concentrated than levels found in typical siloxanes. This material was dissolved in CC14 at about 1/10 the normal dilution for a siloxane polymer. Thus, the total OH present in the CC14 solution corresponds to a PDMS sample having 3750 ppm OH, which is at least several times higher than normal PDMS values. This is also in the range where intermolecular OH-to-OH H-bonding occurs. The spectrum of this material dissolved in CC14 is shown in Fig. 4a. The large broad feature near 3500 cm -1 is indicative of H-bonding and attests to the high silanol concentration. A spectrum of the material following deuteration with a single application of D20 is shown in Fig. 4b, and there has clearly been a very large reduction in the OH absorbances along with a corresponding increase in the OD absorbances. A second application of D20 yields the spectrum in Fig. 4c, which shows a slight OH decrease from Fig. 4b. Figure 4d is the spectrum following a third application of D20 and shows no difference from Fig. 4c. The absorbances seen in the spectra of Figs. 4c and 4d correspond to residual CH vibrations. There is no detectable silanol and, compared to Fig. 4a, essentially complete deuteration of the silanol species has occurred. In all work presented in this paper two applications of the D20 are used to ensure complete deuteration. It turns out that two applications are also necessary to convert all the water in the system to D20 and avoid any traces of HDO. This obviates the need for the spectral subtraction of HDO which would otherwise be necessary. Deuteration of silanol groups produces a smaller per482

FIG. 5.

These are spectra of the isolated silanol features from three

differentPDMS samples: (a) 1000cS, (b) 35 cS, and (c) cyclictetramer. Spectral subtractionof D20 has been performedon each. Althoughnot necessary for a and b, it does improve the baseline for low-silanol materials such as c. turbation to the siloxane backbone than does H-bonding of the silanol groups to a polar solvent. This is because H-bonding causes a distortion of the electron cloud on the H atom, and the effects of this are felt, to a small level, back to the Si atom to which the hydroxyl is attached. This is partially the reason why the detection limit for the H-bonding approach is larger than the noise level of the measurement. Deuteration, on the other hand, produces more of a mechanical effect, in that there is no fundamental change in molecular bonding and, hence, no change in the strength of the vibrational oscillator. Additionally, as was mentioned earlier, an OH stretching vibration is already somewhat isolated from the bulk of a molecule due to the small size of H and D relative to other atoms. The upshot of this is that the deuteration approach produces a modified material in which the underlying polymer structure remains more similar to the original than does that which occurs in the H-bonding approach, and the background features can be more completely removed by spectral subtraction. This then allows a lower detection limit, one which approaches the noise level of the measurement. Figure 5 shows the spectra of isolated silanol features for the 1000- and 35-cS materials shown in Fig. 2 and also for a cyclic PDMS tetramer. The 1000- and 35-cS materials have measured silanol levels of 503 and 112 ppm, respectively, consistent with the H-bonding and chemical methods. The cyclic material is found to have 20 ppm. This 20-ppm spectrum in Fig. 5c shows a baseline free of artifacts down to the noise level of the measurement, and it can be concluded that deuteration produces no measurable change in the underlying combination bands. From this result a detection limit of 10 ppm is estimated for the deuteration technique. Replicate measurements on these samples gave a relative precision of about 2% for higher levels and 20 % for lower ones.

Volume 45, Number 3, 1991

In the H-bonding approach, spectral measurements on four separate solutions and five spectral subtractions are required in order to isolate the silanol features. In addition, the subtraction of water in the presence of a H-bonding agent can be fairly subjective. In the deuteration procedure, only one sample solution and two spectral subtractions (three if the SiOD features are also isolated) are required, and both subtractions can be performed with little subjectivity. The subtraction of protonated and deuterated spectra (Fig. 3) is easy to perform since the concentration of siloxane is essentially identical in the two measurements. The subtraction factor is always very close to 1.00, and is readily adjusted with the use of common CH features in the 4200-4500 cm -1 region. The subtraction of water is unchanged from previous work. 2 The water peaks are sufficiently resolved from the silanol absorbances to be easily subtracted. Although both of these subtractions are easily done manually, they can also be automated to eliminate human interaction. One simple way of doing this is by using first-derivative spectra. Peak heights in this instance are measured as the distance between positive and negative lobes for a particular absorbance, thus eliminating the need to estimate a baseline, and optimum subtraction factors are found by ratioing peak heights of common features between the two spectra in the subtraction. Like the H-bonding method, the deuteration technique is immune to most impurities. Only labile H will generally be affected. For impurities such as these, interference with the silanol measurement may still not be severe. NH stretches are significantly lower in frequency than silanols, and COH absorbances are about 50 cm -1 lower or more. The presence of these species would obscure the silanol measurement only if their concentration were much higher than that of the silanol. The deuteration technique is readily applicable to siloxanes with other functional groups present. A few examples are shown in Fig. 6. These materials produce spectra comparable to those of PDMS except that the nature of the internal H-bonding is somewhat different, as evidenced by a change in appearance of the broad feature near 3600 cm-L Figure 6a, hydrogen silsesquioxane resin, is a good example of how most impurities have no effect on the measurement. This sample was presented as a 35% solution in toluene. Even though the sample is 65 % toluene, there is no evidence of toluene absorbances in the final spectrum.



3900 3600 3700 3600 3~00

3 ~ 0 0 3~00 3~00

FIG. 6. Isolated silanol features from three other siloxane materials, these being (a) hydrogen silsesquioxane (HSiO3/2) resin, (b) a mixture

of methyl vinyl cyclic siloxanes, and (c) a methyl hydrogensiloxane polymer.

1. D. R. Anderson, "Infrared, Raman, and Ultraviolet Spectroscopy," in Analysis of Silicones, A. L. Smith, Ed. (Wiley, New York, 1974), Chap. 10, p. 247. 2. G. W. Griffith, Ind. Eng. Chem. Prod. Res. Dev. 23, 590 (1984). 3. R. B. Taylor, B. Parbhoo, and D. M. Fillmore, "Nuclear Magnetic Resonance Spectroscopy," in The Analytical Chemistry of Silicones, A. L. Smith, Ed. (Wiley, New York, 1991), Chap. 12, p. 347. 4. G. R. Lucas and R. W. Martin, J. Am. Chem. Soc. 74, 5225 (1952). 5. E. Kohn, Polym. Mat. Sci. Eng. 54, 185 (1986). 6. A. L. Smith, unpublished data. 7. G. E. Kellum and K. L. Uglum, Anal. Chem. 39, 1623 (1967).