Infrared Absorption Spectroscopy of Polycarbonate at High Pressure

R. G. KRAUS,∗ E. D. EMMONS, J. S. THOMPSON, A. M. COVINGTON Physics Department and Nevada Terawatt Facility, MS 220, University of Nevada, Reno, Reno, Nevada 89557-0058

Received 16 October 2007; revised 18 December 2007; accepted 19 December 2007 DOI: 10.1002/polb.21405 Published online 4 February 2008 in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: High-pressure Fourier-transform infrared absorption spectroscopy has been performed on polycarbonate, using a diamond anvil cell to produce pressures up to ∼6 GPa. The frequencies of the vibrational modes have been measured as a function of pressure. Individual mode Grüneisen parameters have been determined for six vibrational modes. The data were fit to models that included both volume-dependent and -independent Grüneisen parameters. The vibrational frequency shifts as a function of pressure have been found to be consistent with those measured for similar types of bonds in other molecules. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 734–742, 2008

Keywords: compression; FTIR; high pressure; infrared spectroscopy; polycarbonate

INTRODUCTION
Polycarbonate (PC) has a wide variety of industrial applications including bullet proof glass, compact discs, and common water bottles. A cursory inspection of a piece of PC shows that it is hard, lightweight, and transparent to visible light. These properties also make it useful for applications in research and development. An interesting application is as a window material in laser-driven shock wave experiments. A good description of this type of experiment and the uses of the backing window can be found in a recent publication by Swift et al.1 Under the conditions of this type of experiment, PC would reach high temperatures and pressures as dictated by the shock Hugoniot. PC has been previously studied with Raman spectroscopy at static pressures up to 35 kbar in
∗ Present address: University of Cambridge, Emmanuel College, Cambridge, CB2 3AP, UK Correspondence to: R. G. Kraus (E-mail: richardgkraus@ gmail.com) Journal of Polymer Science: Part B: Polymer Physics, Vol. 46, 734–742 (2008) © 2008 Wiley Periodicals, Inc.

a diamond anvil cell (DAC).2 The infrared absorption spectrum of PC has not previously been measured as a function of pressure. Data from these measurements can be used to calibrate ultrafast infrared reflection spectroscopy diagnostic techniques. These diagnostics are used in shockcompression experiments, as has been done in the case of nitrocellulose3 and poly(vinyl nitrate),4 to determine shock pressure and the effect of shock waves on chemical bonds. Only a limited number of vibrational spectroscopy experiments have been performed on polymers at static pressures typically achieved in a DAC. For a thorough literature review regarding vibrational spectroscopy of polymers at high pressure, see Emmons et al.5 We have measured the Fourier Transform infrared (FTIR) absorption spectrum of PC at high pressures up to ≈6 GPa in a DAC. The FTIR absorption spectrum of PC at room temperature and 1 bar of pressure has been studied previously, and the vibrational modes have been identified by Silverstein and Bassler6 and Schnell.7 Individual vibrational mode Grüneisen parameters have been determined under the assumption that they are volume-independent. In addition, the data

734

the coefficient of thermal expansion β. i A substitution can then be made for dνi /dV in eq 3 so that p=− 1 dEpot + dV V γi hνi i GRÜNEISEN PARAMETER ANALYSIS AND VIBRATIONAL ANHARMONICITIES Data from high-pressure vibrational spectroscopy experiments is typically analyzed to determine individual mode Grüneisen parameters.9 The bulk Grüneisen parameter γ relates the bulk volume of the sample V . It is possible to show that the Grüneisen parameter can be written as γi = − d ln(νi ) V =− d ln(V ) νi dνi dV . (9) where B(T) is the Tait parameter12 in GPa with the temperature in K given by B(T) = (0. Substituting back into eq 1. is independent of volume. V (0) To determine the value for V (P) one can use the equation for the bulk compressibility of PC determined empirically by Zoeller. and the bulk modulus B of a given material by the equation BV β . 2 exp(hνi /kB T) − 1 (6) The summation can then be done over the individual modes. V (2) wherein the pressure is determined by the following relation. much of the error in using the Mie-Grüneisen equation of state is in the knowledge of the bulk Grüneisen parameter.12 V (0) P(GPa) = 1 − (0. the heat capacity CV .2 During data analysis.INFRARED ABSORPTION SPECTRA OF POLYCARBONATE 735 have been fit to a model where the mode Grüneisen parameter is assumed to be proportional to the fractional change in volume of the sample. The complete set of individual mode Grüneisen parameters must first be found and then the bulk Grüneisen parameter can be determined through the summation of individual mode Gruüneisen parameters in eq 6. The volume coefficient for thermal expansion β is defined as β= 1 ∂V V ∂T =− p 1 ∂V V ∂p T ∂p ∂T = V 1 ∂p B ∂T . Using this expression and assuming that the individual mode Grüneisen parameter. A simple assumption can be made that νi = V −γi . (10) Information about the intermolecular potentials and the nature of the compression can be determined through the value of the mode Grüneisen parameter.8. (4) where γi is the individual mode Grüneisen parameter. Epot is the temperature-independent potential energy associated with the interatomic interactions. one can see that β= γ BV δEmodes δT = V γ CV .0894) ln +1 V (P) B(T) −1 with the summation over each individual mode at frequency νi . this type of determination of the bulk Grüneisen parameter is difficult because of the high number of vibrational modes in most polymers. leaving p=− γ Emodes dEpot + . In practice.002609T]. particular emphasis was placed on the effects of the removal of free volume in the sample. then γi is the slope of the plot of ν (P) V (0) ln νi (0) versus ln V (P) . the mode Journal of Polymer Science: Part B: Polymer Physics DOI 10. For example. p=− dEpot − dV h i dνi dV 1 1 + 2 exp(hνi /kB T) − 1 (3) Bulk Grüneisen parameters are extremely important in modeling the mechanical properties of solids and liquids. γ = CV (1) 1 1 + . BV (8) The complete derivation for this relation can be found in Hook and Hall10 and a summary of the derivation follows. γi .11 Note that in this IR absorption experiment the bulk Grüneisen parameter was not calculated.1002/polb . (5) . dV V (7) where γ is now the bulk Grüneisen parameter. Bulk Grüneisen parameters are useful for calculating thermal energies in shock-compression experiments using the Mie-Grüneisen equation.3878) exp[−0.

A liquid nitrogen cooled mercury cadmium—telluride detector was used to detect the radiation. the vibrational frequency is independent of pressure and density changes. As opposed to KBr.18 and was found to be qualitatively hydrostatic up to 7 GPa. which was used as the pressure transmitting medium in ref. An amorphous solid is usually of lower density than a crystalline solid of the same polymer. the mode frequencies of PC shifted by an amount on the order of 1% from the zero-pressure values. vibrational bands decrease in intensity and shift to higher frequency as the pressure is increased. If the slope ν (P) V (0) of the plot of ln νi (0) versus ln V (P) is a coni stant. where the chains are moving closer together and the bonds decrease in length with compression.07) is more closely matched to diamond (2.0 µm (5000 cm−1 ).37) than that of KBr (1.1002/polb for some Raman active modes of PC. IR radiation was produced in a globar lamp. Once the majority of void spaces are removed. AZ) designed for performing Raman and FTIR absorption measurements at moderate pressures. the light is then passed to the FTIR spectrometer. the changes in bond lengths for the stretching modes were of the order of 0. identical to the first reflecting condenser.5 These indices were measured at 2. Tucson. A second objective. AgCl was chosen because the index of refraction (2. the volume changes of the sample were ≈25%.5 and Dattelbaum et al. The culet diameter is 0.15 AgCl has been used as early as 1965 as a pressure medium in compressible gasket devices.13.13. In contrast.13 Generally. A more thorough explanation of this phenomena can be found in a previous study by Emmons et al.14 predicts that if the bond lengths decrease by 1%.5 The model of Sherman13. for the final pressures of around ≈6 GPa in the present experiment. for typical potentials the vibrational frequencies will increase by an amount on the order of 10%. as described by Chai and Brown. This explains the tendency for the corresponding vibrational frequencies to increase with compression. the change in the volume must be primarily because of the removal of free volume and compression of the interchain bonds. where AgCl was used as the pressure medium. is used above the sample to recollimate the transmitted light.6 mm.16 It has been noted by Jayaraman et al. The spectrometer was operated in 4 cm−1 resolution mode in the 500–4. EXPERIMENTAL Experiments were performed using a Bruker Hyperion 2000 infrared microscope coupled to a Tensor 27 FTIR spectrometer.17 that AgCl is hydrostatic up to 5.14 involving fairly general potentials. The first stage of compression of an amorphous polymer takes up these void spaces and has little effect upon bond lengths.5 GPa and the hydrostatic nature of AgCl has been explicitly and thoroughly studied by Piermarini et al. and not to compression of the intramolecular bond lengths. γi = m V V (0) =m 1− V (P) . For a purely harmonic potential.000 cm−1 region. and the sample chamber was a hole of ∼250 µm diameter drilled in an Inconel gasket. where m is a parameter that determines the volume dependence and V is defined as V (0) − V (P). Clearly.1%. 5. From models such as that of Sherman. thus effectively eliminating the etaloning effect seen by Emmons et al.9 found that most volume-dependent modes will reach a critical value of the compression and thereafter the mode will appear volume independent. As will be shown later. The DAC used was a four-post high-pressure cell (High Pressure Diamond Optics. Emmons et al. if the slope is not constant. V (0) (11) anharmonicities.19 The shift of the R2 line depends only on the mean stress (pressure).14 so pressure-induced shifts of the vibrational frequencies indicate bond . the scan was repeated 1000 times at each pressure to improve statistics. The standard ruby fluorescence technique was used to measure the pressure. and knife edge apertures were used to truncate light to the area of interest. because the random orientations of the polymer chains cause void spaces to form. then the mode Grüneisen parameter is considered to be volume dependent. The nature of the stresses in a pressure medium can be determined by examining the spacing and widths of the ruby R1 and R2 lines. A reflecting condenser was used to focus the IR radiation on the sample. the compression of the polymer will start to look more like that of a crystalline polymer. Flores and Chronister2 assumed a volume-dependent mode Grüneisen parameter to have the form. the potential gradients tend to increase as the internuclear distance is decreased. while Journal of Polymer Science: Part B: Polymer Physics DOI 10.736 KRAUS ET AL. Grüneisen parameter can be dependent on or independent of the volume of the sample. Thus.53). In contrast. then the mode can be considered to be volume independent.

Spectrum of PC at ambient pressure and temperature. The PC sample was not characterized to determine properties such as the glass transition Journal of Polymer Science: Part B: Polymer Physics DOI 10. PC contains no vibrational modes in this range. as the size and positioning of the AgCl slabs was not well controlled. This could be caused by a heterogeneous distribution of the pressure medium within the sample chamber. The mass of the monomer is 254.21 The PC samples (Sigma-Aldrich. Further characterization was not given by Flores and Chronister. temperature. The thickness of the films varied between ∼5 and 100 µm. as determined by comparison to the thickness of the gasket.000. the maximum pressures obtained were ∼6 GPa. Type IIa diamonds were used in the DAC in order to minimize impurity induced one-phonon absorption. and decrease in intensity as the pressure is increased. All of the vibrational modes inhomogeneously broaden. Schoonover et al. and the average mass of a polymer chain is 198.20 The range from 1900 to 2300 cm−1 could not be studied because of strong absorption.1002/polb The chemical structure of the repeating PC monomer unit is illustrated in Figure 1. Thicker films were studied to examine the weaker absorption bands while thinner films were studied to prevent the stronger absorbing peaks from saturating. Uncertainty in determining the average pressure within the sample volume can be due to a quasihomogeneous pressure distribution across the diamond culet.22 The PC used in the high-pressure Raman spectroscopy study by Flores and Chronister2 was likely similar. PC of this type typically has a glass transition temperature of ≈145 ◦ C and a melting point of ≈233 ◦ C. with contributions from the three effects described earlier. This spectrum was obtained by casting a thin film of PC using dichloromethane (CH2 Cl2 ) as a solvent. Chemical structure of the monomer of PC. The mode labels given in Table 1 correspond to those shown in Figure 2. and thin films were formed across the sample chamber of the inconel gasket. Identification of several infrared modes studied under high pressure is given in Table 1.20 Fortunately. By observing ruby line broadening. The 1800–2600 cm−1 region has been removed because there are no vibrational modes in this spectral region. AgCl was then used to fill the remaining volume of the sample chamber. shift to higher frequency. for they were cut and positioned manually.INFRARED ABSORPTION SPECTRA OF POLYCARBONATE 737 Figure 1. melting point. RESULTS the splitting of the two lines varies depending on whether the ruby crystal is being compressed parallel to the c-axis or the a-axis. The infrared absorption spectrum of PC at ambient temperature and pressure is shown in Figure 2. Similarly. changes in splitting. the estimated errors in the pressure are ∼5%. and different ruby crystals within the sample volume.000) consisted of a variety of thin film thicknesses. and free volume content.23 attributed the broadening of the peaks to pressure Figure 2. In the present study using AgCl as a pressure medium. The 1800–2700 cm−1 region has been omitted because of overcompensation of the diamond absorption background subtraction. Representative infrared absorption spectra of PC as a function of pressure for the vibrational modes in the range of 800–1600 cm−1 are shown in Figure 3. . the infrared absorption spectrum in the region of the O–C–O stretch mode from 950 to 1060 cm−1 is shown in Figure 4. Broadening of the ruby lines is due to spatial variations of the mean stress across the ruby chip. PC was put into solution by dissolving small amounts of the material in dichloromethane (CH2 Cl2 ). The labels above several of the peaks are references to their mode descriptions in Table 1. average molecular weight 198. with the production of two phonons that is present in a perfect diamond lattice.

variations within the DAC and to the molecules being locked into different bond lengths. The infrared absorption data from a C C C deformation are shown in Figure 7.738 KRAUS ET AL. the frequency differences become accentuated. Figure 5. (deformation) refer to bending modes. Table 2. Journal of Polymer Science: Part B: Polymer Physics DOI 10. and this absorption feature clearly exhibits low-pressure volume dependence and high-pressure volume independence to its mode Gruneisen parameter. Table 1. pressure variations within the DAC also contribute to the peak broadening. In the high-pressure regime. Plot of shift in frequency with pressure for methyl antisymmetric C–H stretch. Because of the increased interchain interactions at high pressure. Infrared absorption spectra of PC for a symmetric O–C–O stretching mode.9 was used. the polymer chains are pushed closer together and the Figure 3.7 The symbol ν refers to stretching modes. bond angles. The peak position was determined by the peak maxima method. In the low-pressure regime. Table of Infrared-Active Vibrational Modes Analyzed at High Pressure Label 1 2 3 4 5 6 Frequency (cm−1 ) at Ambient Pressure 831 1015 1080 1505 1772 2970 Assignment Out of plane (C H) def. In the present experiment. and local environments as the pressure is increased. increase in width. This technique assumes that there are two different regimes involved in the compression. γ and def. The intensity of all the vibrational modes monotonically decrease in absorbance as the pressure is increased. Plots of the data converted to units of ν (P) V (0) ln νi (0) versus ln V (P) for several other modes i are shown in Figure 6.1002/polb . and estimated error bars are shown to within ±2 cm−1 and 5% of the pressure. Mode Grüneisen parameters were found for several of the infrared active modes of PC. and shift to higher frequency of the mode with increasing pressure. Parameters for both the volume-independent and volume-dependent models of the Grüneisen parameters are given in Figure 4. νs (O C O) γ (C C C) Ring ν(C C) ν(C O) Methyl νa (C H) combination The assignments were found by Silverstein and Bassler6 and Schnell. A plot of the infrared absorption data for the 2970 cm−1 methyl antisymmetric C H stretch is shown in Figure 5. Infrared absorption spectrum of PC as a function of pressure for the range 800–1600 cm−1 . the compression mainly involves the removal of free volume. An analysis technique similar to that of Dattelbaum et al. This figure shows the decrease in intensity.

The value of ν/ P measured between ∼ 6 GPa and ambient pressure is also listed. This graph shows the tendency for certain vibrational modes to exhibit both volume-independent and -dependent mode Grüneisen parameters.7 ± 0. and the high pressure fit to a linear slope is shown by a solid line.0 ± 0.1 1.2 ± 0. To determine the frequency of the peak by a fit function.1 2. consistent with the measurements of Dattelbaum et al. For regions of high mode density. the data points below a particular pressure were excluded from the fits. The final V (0) column lists the intercept with the ln V (P) -axis of the volume-independent fit. although it varies from mode to mode.027 ± 0.155 ± 0. and Volume-Dependent Parameters. The labels correspond to the modes listed in Table 1.1 2.5 GPa. Peaks which exhibit volume-dependent mode Grüneisen parameters are fit as shown with the dashed line. All of the modes were found to have volume-independent Grüneisen parameters in the higher pressure regime. In these regions. Journal of Polymer Science: Part B: Polymer Physics DOI 10.3 ± 0. This method was determined to be viable based upon comparisons made on peaks in which both methods were possible. Table of Volume-Independent Grüneisen Parameters.047 ± 0.2 0.5 0 1. the peak position was determined by finding the frequency of the peak maximum.7 ± 0.9 For absorption peaks in regions of low mode density. bond lengths are starting to decrease. for a crosslinked poly(dimethylsiloxane). since for some modes the initial compression caused a decrease in void space and not bond length. the peak Table 2.003 0.9 The interV (0) cepts of the linear fits with the ln V (P) axis are also listed in Table 2.3 Uncertainties result from fitting the volume-dependent and -independent fitting functions to the V (0) ln ν(P) versus ln V (P) data.1002/polb .004 ν/ P (cm−1 /GPa) 1.004 – 0.004 0. they often broaden to show Gaussian features when the sample is pressurized nonuniformally.7 ± 0.095 ± 0. Infrared absorption features are nominally Lorentzian in shape.062 ± 0. This particular pressure was often around 1.2 Pressure (GPa) 0 0.006 0.9 ± 0. one would have to use a large number of parameters to fit the complicated spectra.001 0. Plot of ln νi (P) versus ln V (P) for all peaks νi (0) analyzed.006 0.7 ± 0. γi . however.3 0. converted back to pressure units. Values of the ν(0) volume-dependent parameter m were not calculated for modes that are obviously volume independent. use of a fitting function was not practical owing to large number of peaks and etaloning around the absorption feature of interest.INFRARED ABSORPTION SPECTRA OF POLYCARBONATE 739 V (0) Figure 6.2 ± 0.056 ± 0.2 8.117 ± 0.003 0. the peak centroid could be found by fitting the data to a Voight profile function. increasing the uncertainty beyond that which is acceptable. These give a relative indication of the pressure where the free volume in the polymer is removed. m Label 1 2 3 4 5 6 γi 0.1 2.169 ± 0.006 m – 0.041 ± 0. To determine the volume-independent Grüneisen parameters.218 ± 0.003 0.7 ± 0.

740 KRAUS ET AL. This was interpreted to be due to shielding of the modes on the polymer backbone from the initial stage of the compression.12 from which the equation of state was obtained. however.2 For the modes measured. Flores and Chronister performed Raman spectroscopy of PMMA and PC at high pressure in a DAC. as to how accurate one could be in determining the centroid position. DISCUSSION Amorphous polymers contain a significant amount of free volume because of inefficient packing of chains in the solid. however. while those on the polymer backbone had volume-dependent parameters. maxima method was found to consistently agree to within the fitting errors of the Voight fitting function. Representative error bars are also shown (see text for details). The relative uncertainty in the pressure measurement was determined to be about 5%. Other studies of the free volume as a function of pressure have also been performed.5 found that this does not hold for all the vibrational modes of polymers. For higher molecular weight samples with less free volume. reasonable assumptions were made. where compression of the free volume is important. This is qualitatively in agreement with the GibbsDiMarzio theory. V (0) Figure 7. As a result. and thus the glass transition temperature. The effect of high pressure on the free volume is of fundamental interest and has received attention in several studies.24 The molecular weight of a polymer effects the fractional free volume. However. since above the glass transition temperature there is enough free volume in the polymer to allow the coordinated motion of polymer chains. It was found that the glass transition temperature asymptotically approached a limiting temperature of 485 K as the pressure was increased. the glass transition temperature generally increases with increasing molecular weight. based on the width of the absorption feature.1002/polb . based upon a test run in which multiple ruby chips were placed at different locations that spanned the sample chamber. as described by Sperling. Figure 5 shows the shift of peak position with pressure for a methyl antisymmetric C–H stretch in which the peak positions were determined by the peak maxima method. Higher molecular weight materials would be less compressible at low pressures than low-molecular-weight materials. the mode Grüneisen parameters would be expected to have a smaller volume dependence. Due to decrease of free volume with increasing molecular weight. were not known. This graph shows the tendency for certain vibrational modes to exhibit both independent and dependent mode Grüneisen parameters. it would also be expected that the equation of state is a function of molecular weight. Dattelbaum et al. Measurements of samples of different molecular weights where the fraction of free volume has also been characterized by a technique such as positron annihilation lifetime spectroscopy would be helpful in elucidating these effects. the uncertainty in the peak position was determined from the fitting error itself. For those peaks that were fit to a Voight fitting function. Plot of ln νi (P) versus ln V (P) for C–C–C νi (0) deformation. where the main process is removal of the free volume.25 Materials with higher molecular weight have fewer end groups. and consequently less free volume. The pressure measurements from each of the ruby chips were compared after increasing the pressure and found to agree within ≈5%. Skorodumov and Godovskii24 measured the glass transition temperature of PMMA as a function of pressure. Journal of Polymer Science: Part B: Polymer Physics DOI 10. which predicts that the glass transition temperature should increase indefinitely as pressure is increased.9 and Emmons et al. and those used by Zoeller. Free volume is connected to the glass transition. it was found that modes off the polymer backbone had volume-independentmode Gruneisen parameters. Calculating the uncertainty in centroid position for those peak positions which were determined by the peak maxima method is a bit subjective. The fractional free volumes of the samples used in the present study. and in contradiction to the free volume theory.

2 Two of the six vibrational modes analyzed. respectively. respectively) found by Schoonever et al. The mode Grüneisen parameter related to peak 6. m. 0.72 cm−1 /GPa.047 ± 0. Four out of the six vibrational modes analyzed in this experiment. however. It is also possible that the difference in Grüneisen parameter between modes 1 and 5 could be due to the inherent difference in the type of vibration: mode 5 is a double-bond stretch. Flores and Chronister2 found m to have a value of 0. 10.095 ± 0. polyester. the methyl antisymmetric C–H stretch is relatively far from the backbone and would not be shielded from the initial compression. it is difficult to say how these vibrations will act and there is very little theoretical support for this type of experiment.18 cm−1 /GPa. The data indicate that most of the polymer free volume is removed after .23 to shift by 12. CONCLUSIONS The frequencies of the infrared absorption modes of PC have been measured as a function of pressure in order to determine mode Grüneisen parameters. 6.26 pointed out that the arrangement of polymer chains in a solid can also contribute to variations in measured values of Gruneisen parameters. equal to 0. and 10 cm−1 /GPa. and degraded estane which where found by Schoonever et al.027 ± 0. and 6 from Table 1 were found to show some volume dependence. and it has been shown that using a model in which the Grüneisen parameter is proportional to the fractional change in volume gives a better fit to the experimental data in these cases.2 The value of the volume-independent Grüneisen parameter for each mode is significantly different (0. The 1772 cm−1 C O stretch was found to exhibit a shift with pressure of 2. is nearly double that of the other modes which exhibited initially volume-dependent Grüneisen parameters. since the equation of state will change. 3. peaks 2. peaks 2. it is within the range of pressure-induced shifts of a C–H stretch in polyurethane. in the volume-independent region (0. the equation of state and pressure-induced vibrational frequency shifts could depend on the sample pedigree. and this is greater than the pressure-induced shift of 6. Under compression. 4. However.INFRARED ABSORPTION SPECTRA OF POLYCARBONATE 741 Wu et al. polyester.006). 3 cm−1 /GPa. to see if general trends can be established. estane.001 for mode 1. were found to have purely volumeindependent mode Grüneisen parameters. Both of these modes can be considered off the backbone and thus is in agreement with the conclusions made by Flores and Chronister. this could be caused by a greater anharmonicity of the local potential surface or a larger local compression for mode 1. For example. As stated earlier. Variations in samples such as differences in the percent crystallinity or the fraction of free volume in the amorphous phase will change the measured value of the Gruneisen parameter. it is possible that the local potential surface for mode 1 shows a greater Journal of Polymer Science: Part B: Polymer Physics DOI 10.23 Some of these results are inconsistent with the explanation provided by Flores and Chronister2 that vibrational modes off the polymer backbone are often volume independent. This could be caused by a greater anharmonicity of the potential surface or a larger local compression of the methyl antisymmetric C–H stretch. modes 1 and 5. Some care must be used. since the modes are not pure vibrations and the nature of the polymeric material will also play a role. In general. 2. and 4 are close to or on the backbone and might be shielded from the initial compression. and degraded estane (3. 2. which is in agreement with the analysis done by Flores and Chronister. 1).1 cm−1 /GPa for a methyl C–H stretch of PMMA. In this instance.23 The 1015 cm−1 O–C– O stretch was found to have a volume-dependent parameter. whereas mode 1 is an out-of-plane deformation. this phenomena was also noticed by Schoonover et al. Most of the analyzed vibrational modes of PC have volumedependent Grüneisen parameters.191 for the Raman active O–C–O stretching mode in PC. It is also useful to compare the pressureinduced shifts of the vibrational modes in PC to similar modes in other polymers.5 However.155. Because there is no large difference in distance between the backbone and these modes. yet it shows a strong volume dependence. it is plausible that the methyl antisymmetric C–H stretch sees a larger local compression because of the relatively large distance of this mode from the polymer backbone (see Fig. This is in agreement with the pressure-induced frequency shift for a C O stretch in polyurethane.003 for mode 5). estane. 3.1002/polb anharmonicity than that of mode 5. The 2970 cm−1 methyl C–H combination stretching mode exhibits a shift with pressure of 8. Data of this type on scientifically and technologically important materials is helpful for benchmarking theoretical models of the materials under pressure and interpreting the results of shock-compression experiments.

18.0 GPa..-K. J Appl Phys 2003. 9. H. D. W. 144903. 1991. Moore. Although they cannot be definitively ruled out.-N. 1605. 9342. J Phys C Solid State Phys 1980. D. 358. C. McGrane. and W. Overall. Niemczura. R. Bridgewater. 29. C. Walker.html. compression to 1. 737. 127. Raizer. Kober. We also thank the UNR physics department electrical and mechanical technicians B.als. 108. J. H.. McGrane. Wu. Block.3. Appl Spectrosc 2004. Zel’dovich. Piermarini. A. 8. Wiley: Hoboken.. B. E. Cline. Narayanamurti. F. Introduction to Physical Polymer Science. 10. New Jersey. Kraus. 4601. A. D. Jayaraman. B.. Meredith. M. 13. This technique has been used to study nitrocellulose3 and poly(vinyl nitrate)4 under shock compression. 42. M. Chem Phys Lett 1973. Moore. Brinsmead. 4348. 1964. Luo. J.. S. 374. J. I. Jura. 093907. 368. 27. 17. Y. Godovskii. Barnett. Solid State Physics. 10. J Chem Phys 2005. E. 58. L. 491. J. Bassler. G.gov/IRwindows. J Phys C Solid State Phys 1982. P. L. 19. W. Bourne. Geophys Res Lett 1996. J.. 28. 26. Tierney. Wiley: New York. 3539. 76. there has been increased interest in recent years regarding the high-pressure properties of polymers and energetic materials. Covington. 15. there is no evidence for any phase transitions such as crystallization in the measured experimental data.28 This work was supported by the Honors Undergraduate Research Award at the University of Nevada. Rev Sci Instrum 2005. 2002. Weaver for technical assistance. M.. Willis. The pressure-dependent shifts in the vibrational frequencies were generally found to be consistent with those measured for similar bonds in other polymers. Emmons.-K. Swift.polymersdatabase.. F. D. D.. G. 4. C. V. III. 309. J. H. Bucher..lbl. N. J. Nicol. J Phys Chem A 2004.. J. Zoeller.9. K. J Polym Sci Polym Phys Ed 2007. W. S. D. J Appl Phys 1973.. Private communication. R.. 43. H.. M. P. Raman spectroscopy is a common ultrafast in situ diagnostic technique for shock-compression experiments. M. Journal of Polymer Science: Part B: Polymer Physics DOI 10. 21. Menikoff. 6. D. Dattelbaum. Sherman. S. J.. Hendra.1002/polb . H. S. 45. J. Paisley. J. Wu. R. A. especially those commonly used in shock-compression experiments. D.4. 153. As the shock pressures become higher. S. Chronister. Lewis. G. Y. D.. M. 14. 20. K. Jensen. V. J. 1453. C.. Dattelbaum. J. S. Funk. W.. Funk. sample heating will also become more important. J. 4th ed. E. J Sci Instrum 1965. Duvvuri. J. 25. Silverstein. Dover: Mineola. 15. J. 22.. D. 24. Shen. Physics of Shock Waves and High-Temperature Hydrodynamic Phenomena. Chai. Tim Darling for many fruitful discussions. W.. J Appl Phys 1972.. as might be indicated by peak splittings or discontinuous changes in the frequencies or in dν/dP as a function of pressure. Elsevier: New York. S. 3. Brown. E.. 16. Gray. D. Sperling. M.. 13. 1963. 20. Schoonover. A. but ultrafast infrared reflection measurements have been performed as well. 27. E. F. 2007. Polym Sci USSR 1987. Hook. L. E. REFERENCES AND NOTES 1. D.. 23. J. T. M. 42. 7. Rep Prog Phys 1979. III. M.. 2.... 2006. 5. Schnell. G. Poly(vinyl nitrate) was observed to undergo a chemical reaction on picosecond time scales during shock compression to ≈18 GPa. King. G. 12. 9. We sincerely thank Dr. and the US DOE under Grant no. Spectrometric Identification of Organic Compounds... Maines. G. D.. Sherman. 122.742 KRAUS ET AL..com.. G. Swift. DE-FC52-06NA27616 at UNR. Spectrochim Acta 2003. Osborn. R..27 Static high-pressure data of this type is particularly valuable for analyzing experiments using ultrafast vibrational spectroscopy as a diagnostic during shock-compression experiments. M. Schwendt.. 21. Polymer 1968. 149. Chemistry and Physics of Polycarbonate. Thompson. 44. Johnson. S. Interscience: New York. 59. J. Hall. 93. R. 11. Phys Rev Lett 1970. Kenney. and it will be necessary to perform static measurements as a function of both pressure and temperature.. http://infrared. 25. Flores. D. C. P. S. J Polym Sci Polym Phys Ed 1982. New York. Static data of the type measured in the present study would be useful for benchmarking these shockcompression diagnostics. T. J Raman Spectrosc 1996. S.. R. V. 23. 5377.. http://www. Reno.. J. D. Y. R. Zichy. IV.. 8966. Skorodumov.