Structure-Property Relations in Polymers - ACS Publications

This long-wavelength cutoff excludes the investigation of longitudinal acoustic modes in lamellar polymer structures (4, 7). The Raman spectra present...
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2 Vibrational Spectroscopy of Polymers Analysis, Physics, and Process Control H . W. Siesler Department of Physical Chemistry, University of Essen, D 4300 Essen, Germany

Improvements in rapid-scanning Fourier-transform infrared (FTIR) spectroscopy, the recent introduction of Fourier-transform Raman spectroscopy, and the more efficient exploitation of the near-infrared region launched vibrational spectroscopy into a new era of polymer chemical and physical applications. On the one hand, increased sensitivity led to breakthrough sampling techniques such as photoacoustic spectroscopy and diffuse reflectance measurements; on the other hand, improved time resolution largely enhanced the potential of FTIR spectroscopy for on-line combination with other techniques such as gas and liquid chromatography or thermal analysis. Significant progress also has been made in the characterization of time-dependent phenomena by the simultaneous acquisition of spectral and other relevant physical data (e.g., during mechanical measurements). Furthermore, multivariate data evaluation, which was restricted to near-IR multicomponent analysis of agricultural products for more than a decade, is increasingly applied in the field of polymer analysis. Last, but not least, the development of fiber optics for the near-IR wavelength range has opened up completely new areas for process control and remote sensing.

\ ^ I B R A T I O N A L SPECTROSCOPY IS AN IMPORTANT TOOL FOR CHARACTERIZATION of the chemical a n d physical nature o f polymers. I n p r i n c i p l e , the c o m p l e ­ mentary techniques o f infrared a n d R a m a n spectroscopy provide qualitative 0065-2393/93/0236-0041$ 12.75/0 © 1993 American Chemical Society

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STRUCTURE-PROPERTY RELATIONS IN POLYMERS

a n d quantitative i n f o r m a t i o n about the following structural details o f a polymer: • C h e m i c a l n a t u r e a n d c o m p o s i t i o n : structural units, type a n d degree o f branching, e n d groups, additives, impurities • S t e r i c o r d e r : cis/trans ( Z / E ) isomerism, stereoregularity • C o n f o r m a t i o n a l o r d e r : physical arrangement of the p o l y m e r chains (planar or nonplanar), regular conformations • T h r e e - d i m e n s i o n a l s t a t e o f o r d e r : crystalline a n d amorphous phases, n u m b e r o f chains per unit cell, intermolecular forces, lamellar thickness • O r i e n t a t i o n : type a n d degree o f preferential p o l y m e r chain a n d side group alignment i n anisotropic materials D e s p i t e the uncontested importance o f vibrational spectroscopy for the characterization o f macromolecular structure, it should be emphasized that only a l i m i t e d n u m b e r o f problems may be solved b y its exclusive application. I n the majority of cases m a x i m u m i n f o r m a t i o n o n the structural details i n question can be obtained only b y an appropriate choice a n d combination o f c h e m i c a l and physical methods. I n this respect the i n t r o d u c t i o n o f rapid-scan­ n i n g F o u r i e r - t r a n s f o r m I R ( F T I R ) a n d F T - R a m a n spectroscopy and the advantages o f these methods over conventional dispersive instrumentation have revitalized the utilization o f vibrational spectroscopy i n p o l y m e r re­ search. I n combination w i t h other techniques a n d the application o f destruc­ tion-free sampling procedures, F T I R a n d F T - R a m a n spectroscopy allow a better correlation o f the spectroscopic data w i t h the results obtained b y other methods f r o m the original sample. T h e intention o f the present chapter is to review some aspects o f m i d a n d near-infrared a n d R a m a n spectroscopy i n p o l y m e r research w i t h special emphasis o n selected examples o f diffuse reflectance measurements, compar­ ison o f photoacoustic F T I R a n d F T - R a m a n spectroscopy, dynamic F T I R characterization o f time- a n d temperature-dependent p h e n o m e n a , a n d the application o f light-fiber optics to process control and remote sensing.

Experimental Details T h e principles, theory, a n d instrumentation o f F T I R spectroscopy have b e e n covered i n detail i n several books a n d reviews (1-4). T h e F T I R spectra presented here were measured o n spectrometers ( N i c o l e t 7199 a n d R r u k e r IFS88). Since the i n t r o d u c t i o n o f laser sources d u r i n g the 1960s, a vast amount o f w o r k has b e e n undertaken using R a m a n spectroscopy to p r o b e a w i d e range o f p o l y m e r i c structures (4, 5-7). C o n v e n t i o n a l R a m a n spectrometers that

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were used to carry out this w o r k generally consist o f a visible laser source, an efficient double o r triple monochromator, a n d a p h o t o m u l t i p l i e r detection system. H o w e v e r , a n u m b e r o f problems are inherent i n the application o f conventional laser R a m a n spectroscopy to p o l y m e r systems. F o r a large p r o p o r t i o n o f samples, irradiation w i t h visible light caused strong fluores­ cence o f additives a n d impurities that was superimposed o n the weak R a m a n signal. A n u m b e r o f (sometimes very time-consuming) approaches were attempted to circumvent this p r o b l e m , i n c l u d i n g p r i o r purification, b u r n i n g out the fluorescence, shifting the excitation fine, o r using p u l s e d lasers. These approaches, at best, have b e e n only partially successful. A further p r o b l e m w i t h conventional R a m a n spectroscopy is that highly c o l o r e d samples o r polymers that contain fillers m a y absorb the R a m a n photons w h i c h prevents the photons f r o m reaching the detector a n d leads to t h e r m a l degradation o f the investigated polymer. T h e foregoing difficulties are some o f the reasons w h y the R a m a n technique is not as familiar as infrared techniques, despite the fact that, i n certain circumstances, R a m a n spectroscopy has a n u m b e r o f advantages over infrared spectroscopy. T h e recent development o f F T - R a ­ m a n spectroscopy (8-12), however, increases the l i k e l i h o o d that this tech­ nique w i l l b e c o m e standard instrumentation i n spectroscopic laboratories. T h e m a i n features o f a n F T - R a m a n instrument are as follows: • a n e o d y m i u m - y t t r i u m a l u m i n u m garnet ( N d - Y A G ) laser, oper­ ated at 1064 n m w i t h a p o w e r output range o f 0 - 2 W • an efficient

dielectric

filter

system to remove the Rayleigh

component o f the scattered radiation • a F T I R spectrometer e q u i p p e d w i t h a quartz o r c a l c i u m fluo­ ride b e a m splitter f o r operation i n the near-infrared region • a photoelectric detector; usually a cooled g e r m a n i u m unit (at 77 K ) o r a n i n d i u m - g a l h u m - a r s e n i d e ( I n G a A s ) detector operating at ambient temperature • a R a m a n sampling compartment w i t h 1 8 0 ° o r 9 0 ° lens-based optics T h e use o f near-infrared excitation confers a n u m b e r o f advantages o n a F T - R a m a n system. B o t h fluorescence a n d self-absorption o f the R a m a n signal are very m u c h r e d u c e d and, d u e to the lower energy o f the exciting fight, t h e r m a l degradation is also less o f a p r o b l e m . A further breakthrough i n this field is the development o f a F T - R a m a n microscope system for small samples i n the m i c r o m e t e r range that offers the application o f m a p p i n g procedures (13). H o w e v e r , c o m p a r e d to conventional R a m a n , F T - R a m a n does have some disadvantages and limitations. It is less sensitive because, d u e to the proportionality o f the R a m a n scattering cross section to the f o u r t h

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STRUCTURE-PROPERTY RELATIONS IN POLYMERS

p o w e r o f the exciting frequency, the shift f r o m the visible to the near-infrared region reduces the intensity o f R a m a n scattering. F u r t h e r m o r e , as a conse­ quence o f detector a n d filter limitations, the R a m a n shift c a n presently only be measured between ~ 3500 a n d 100 c m . This long-wavelength cutoff excludes the investigation o f longitudinal acoustic modes i n lamellar p o l y m e r structures (4, 7 ) . - 1

T h e R a m a n spectra presented here were carried out using a F T - R a m a n accessory ( B r u k e r F R A 1 0 6 ) that was interfaced to the F T I R unit ( B r u k e r IFS88).

Diffuse Reflectance FTIR Studies of the Glass Powder-Coupling Agent Interface of a Composite T h e interface between the reinforcement a n d the p o l y m e r material is o f critical importance to the mechanical properties a n d performance o f compos­ ites, a n d c o u p l i n g agents are u s e d to i m p r o v e the interfacial b o n d i n g (14, 15). Because o f its nondestructive sample preparation procedure, a n d h i g h sensitivity to surfaces, diffuse reflectance F T I R spectroscopy has p r o v e d to b e one o f the most successful techniques to study the reaction of a c o u p l i n g agent w i t h either the resin matrix o r the reinforcement material (16, 17). F r e q u e n t l y , organofunctional silanes are used to promote the adhesion b e ­ tween the inorganic reinforcement a n d the organic p o l y m e r . I n feasibility studies concerning the substitution o f amalgam-based dental filling materials b y glass p o w d e r - p o l y a c r y l a t e composites, vibrational spectroscopy p r o v e d to be an extremely important m e t h o d for investigation o f the glass p o w d e r - c o u ­ p l i n g agent interface a n d the progress o f the photoinitiated c u r i n g o f the m o n o m e l i c diacrylate (18). F o r the composite u n d e r investigation, an a p p l i e d 7-methacryloxypropyltrimethyloxysilane c o u p l i n g agent reacted w i t h the S i O H functionalities o f the glass surface b y condensation a n d f o r m e d bonds w i t h the diacrylate b y polymerization o f the C = C d o u b l e bonds (Structure 1). W i t h respect to a more detailed understanding o f the microstructural changes at the glass p o w d e r - c o u p l i n g agent interface, the diffuse reflectance F T I R spectra o f A e r o s i l O X 50 (average particle diameter 50 n m ; 50 m / g ) were studied as a function o f increasing c o u p l i n g agent coating. A t t e n t i o n was focused o n spectroscopic changes o f n o n - h y d r o g e n - b o n d e d a n d associated S i O H groups o f the glass surface, the increase o f O C H a n d C H functional­ ities, a n d the variation o f the p r o p o r t i o n o f h y d r o g e n - b o n d e d a n d n o n - h y d r o ­ gen-bonded C = 0 groups. T h e amount o f c o u p l i n g agent was characterized b y the organic carbon content d e t e r m i n e d independently b y elemental analy­ sis ( 1 % C corresponded to approximately 100 m m o l o f c o u p l i n g agent o n 100-g glass powder). 2

3

2

T h e spectra were measured i n a diffuse reflectance c e l l ( H a r r i c k ) w i t h K C l as the inert reference matrix [sample:matrix about 1:2 (w/w)] a n d 500

3

3

\ 2

3

II I

DCH 3

agent p o l y mer i nteriace

2

Structure 1. The glass powder-coupling agent-polydiacrylate composite interfaces.

coupling

CH 0-Si-(CH ) -D-C-C=CH / CH Q

i nteriace

g 1 ass

/ ι

-Si-OH

3

CH 0

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STRUCTURE-PROPERTY RELATIONS IN POLYMERS

scans w e r e accumulated at a resolution o f 2 c m ( 0 . 9 6 4 - c m " data point interval). Spectra o f three selected samples w i t h organic carbon contents o f 0, 0.95, and 1.8% are shown i n F i g u r e 1 and reflect the f o l l o w i n g intensity a n d frequency changes w i t h increasing coating ( F i g u r e 2; ν denotes stretching vibration) (18): - 1

1

• T h e intensity of the sharp v ( O H ) absorption (3740 c m " ) o f n o n - h y d r o g e n - b o n d e d S i O H groups decreases drastically ( F i g ­ ure 2a). 1

• T h e intensity o f the v ( O C H ) absorption o f the S i O C H tionalities at 2848 c m increases ( F i g u r e 2b). 3

3

func­

- 1

• T h e intensity o f the v ( C H ) a n d v ( C = 0 ) ( F i g u r e 2c) ab­ sorptions i n the 2900- a n d 1 7 0 0 - 1 7 2 5 - c m regions, due to the c o u p l i n g agent, naturally increase. A n absorption that can be assigned to free C = C resonance stabilized carbonyl groups gradually increases at 1718 c m " at the expense o f the initial v(C=0) b a n d at 1705 c m ( F i g u r e 2d). 2

t o t a l

- 1

1

- 1

a s s o c i a t e d

• T h e v ( O H ) absorption o f h y d r o g e n - b o n d e d S i O H functionali­ ties at 3666 c m "

1

slightly decreases.

T h u s , the mechanism for the chemisorption o f the c o u p l i n g agent at the glass p o w d e r interface can be outlined. I n a first step, the free O H groups o f the glass react completely w i t h the available S i O C H functionalities o f the siliconemethacrylate. A s c o n s u m p t i o n o f free S i O H groups increases, the h y d r o g e n - b o n d e d S i O H groups take over this reaction role (although to a smaller degree) and the percentage o f unreacted S i O C H groups increases. D u r i n g this process the percentage of n o n - h y d r o g e n - b o n d e d C = 0 groups o f the c o u p l i n g agent increases at the cost o f the h y d r o g e n - b o n d e d moieties. 3

3

T h e application o f near-IR spectroscopy to determine the residual C = C d o u b l e - b o n d content a n d enable estimation o f the progress o f the diacrylate c u r i n g process w i l l be discussed i n the section o n near-IR spectroscopy.

FTIR Photoacoustic Spectroscopy Compared

to FT-Raman Spectroscopy

T h e request for r a p i d identification o f u n k n o w n p o l y m e r i c materials w i t h varying morphologies is a very c o m m o n p r o b l e m i n analytical laboratories. D u e to the broader availability o f F T I R instrumentation, the task is often accomplished using infrared spectroscopy even though there are frequently difficulties associated w i t h finding a suitable sampling technique. Photoacous­ tic F T I R as w e l l as F T - R a m a n spectroscopy offer a simple approach to this p r o b l e m . Independently of the morphology, almost any p o l y m e r sample can

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Vibrational Spectroscopy of Polymers

47

α in

a

* * κ ·

α *

0%C

{lien Sen 3

£° _J Q UJ »~i CD · ID *-«

α α 4000

36QQ

3200

2800 2400 WAVENUMBERS

2GGQ

16QQ 12QQ

2000

1600

α in in α Q

jii

0.95%C

(η S Sen ID 1 ° Σ: CM

cc

-j α CD

·

α α 4000

3600

3200

2800 2400 WAVENUMBERS

1200

Figure 1. Diffuse reflectance FTIR spectra of Aerosil OX 50 coated with increasing amounts (0, 0.95, and 1.8% C) of coupling agent. Continued on next page-

American Chemical Society Library 1155 16th St.. H.W. Washington, DC 20036

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STRUCTURE-PROPERTY RELATIONS IN POLYMERS

α in ι Q

α *

3

c

—ι α CQ ·

a

α 10(30

3600

3200

2800 2400 WRVENUMBEBS

2000

1600

1200

Figure 1. Continued. be p l a c e d i n t h e photoacoustic ( P A ) c e l l o r i n the laser b e a m to collect a spectrum i n a matter o f minutes. T o demonstrate the preferential applicabil­ ity o f F T I R - P A a n d F T - R a m a n spectroscopy f o r the destruction-free i d e n t i ­ fication o f p o l y m e r samples, some selected examples w i l l b e discussed after a short i n t r o d u c t i o n to the basic principles o f photoacoustic F T I R spec­ troscopy. T h e photoacoustic effect was first reported b y B e l l i n 1881 ( 1 9 ) , b u t the m e t h o d r e m a i n e d i n the b a c k g r o u n d u n t i l a transducer m o r e sensitive a n d selective than the ear c o u l d b e f o u n d . It was not u n t i l 1973 that a renaissance o f photoacoustic spectroscopy o c c u r r e d ( 2 0 ) , a n d since then numerous interesting applications o f this technique have b e e n r e p o r t e d i n the ultravio­ let, visible, a n d near-infrared regions (21-25). T h e introduction o f F T I R spectroscopy expanded the availability o f P A spectroscopy to the m i d - i n f r a r e d region (25-28) w h e r e it is a p p l i e d quite frequently to the investigation o f polymers ( 2 9 - 3 0 ) . I n F T I R - P A spectroscopy the solid sample is p l a c e d i n a n enclosed c e l l w i t h a n IR-transparent entrance w i n d o w a n d a b u i l t - i n sensitive m i c r o p h o n e ( F i g u r e 3). T h e c e l l contains air or, for increased sensitivity, another c o u p l i n g gas, such as h e l i u m , u n d e r atmospheric pressure ( 2 5 , 31, 32). T h i s c e l l is m o u n t e d i n the sample compartment o f the F T I R spectrometer a n d t h e m i c r o p h o n e takes over the f u n c t i o n o f a conventional F T I R detector. T h e

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Vibrational Spectroscopy of Polymers ω

t/i h£

CsJ

v(OH) f r e e

ω

Q

Q

Ο

α

.00

1.00

2.00

CARBON

3. 0 0

4 .00

m

(a)

ο

en

v(0CH ) 3

Q

α

ο ο

.00

1.00

2.00 3, 00 CARBON t'A)

4.00

(b) Figure 2. Intensity changes of selected absorption bands as a function of the amount of coating represented by the content of organic carbon. Continued on next page.

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STRUCTURE-PROPERTY RELATIONS IN POLYMERS

Figure 2. Continued

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Vibrational Spectroscopy of Polymers

modulated IR-radiation

51

IR-transparent window microphone

pressure fluctuations

air-tight cell

gas _ (e.g. air, He)

w

intermittent heating

sample

Figure 3. Scheme of a PA cell and principle of the photoacoustic effect. sample is irradiated w i t h polychromatic light that is m o d u l a t e d w i t h fre­ quency / : f=2vv

(1)

where ν is the w a v e n u m b e r (per centimeter) and ν is the m i r r o r velocity (centimeters per second) o f the M i c h e l s o n interferometer. W i t h a typical m i r r o r velocity o f 0.1 c m / s , the modulation frequencies vary between 800 and 80 s i n the 4 0 0 0 - 4 0 0 - c m " region, respectively. - 1

1

W h e n radiation o f a certain wavelength is absorbed, the sample is excited to a higher energy level whence it can return to the g r o u n d state b y emission of light or (more c o m m o n l y ) b y nonradiative decay processes or heat release. T h e photoacoustic effect is based o n the heat release p h e n o m e n o n . T h e released heat is transferred to the sample surface at a rate that depends o n the t h e r m a l characteristics o f the sample. D u e to the m o d u l a t i o n of the absorbed light, the nonradiative deactivation processes lead to a p e r i o d i c sample heating that is c o u p l e d into the s u r r o u n d i n g fill gas at the sample-gas interface a n d produces a pressure fluctuation w i t h i n the P A cell. T h e acoustic wave is then propagated through a small connecting passage to the m i c r o ­ phone chamber where the resulting P A s i g n a l — r e c o r d e d as a f u n c t i o n o f w a v e n u m b e r — i s correlated w i t h the optical spectrum. P A spectroscopy has some limitations insofar as the frequency positions of absorption bands are r e p r o d u c e d but the b a n d intensities cannot be interpreted according to the conventional rules o f transmission spectroscopy. T h e signal saturation is a p h e n o m e n o n that is important for understanding the P A effect a n d the interpretation of P A spectra (21, 23, 26, 32-34). T h e amplitude o f the previously m e n t i o n e d periodic heating is decreased b y thermal d a m p i n g processes d u r i n g propagation i n the investigated m e d i u m . It

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S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

can b e shown (21, 23) that only the part o f the sample w i t h i n a d e f i n e d distance f r o m the sample surface contributes to the heat transfer to the surrounding gas (23) a n d the intensity o f the P A signal depends o n the coefficients o f optical absorption a n d t h e r m a l diffusion. I n the practical application o f the P A spectroscopy m e t h o d the spectrum o f carbon-black is r e c o r d e d as b a c k g r o u n d a n d then ratioed against the P A spectrum o f the sample u n d e r investigation. Because o f the lower signal-tonoise ratio f o r P A spectroscopy, longer scanning times ( i n the range o f minutes) are r e q u i r e d c o m p a r e d to transmission spectroscopy. T h e P A spec­ tra presented i n Figures 4, 5a, a n d 6 were taken i n a G i l f o r d - N i c o l e t photoacoustic c e l l w i t h a m i r r o r velocity o f 0.11 c m / s a n d about 500 scans were accumulated w i t h a resolution o f 4 c m (1.928-cm data point interval). Recent r e p r o d u c t i o n o f the data i n a P A c e l l ( M T E C M o d e l 200) o n a F T I R spectrometer ( P e r k i n - E l m e r 1760X) w i t h a m i r r o r velocity o f 0.10 c m / s a n d a resolution o f 8 c m demonstrated that, despite a comparable signal-to-noise ratio, t h e n u m b e r o f scans c o u l d b e p u s h e d d o w n to 32, thereby r e d u c i n g the analysis t i m e considerably (35). -

1

_ 1

- 1

T o demonstrate the potential o f photoacoustic F T I R a n d F T - R a m a n spectroscopy, t h e spectra o f selected polymers i n different morphologies

4000

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800

4 00

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800

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Figure 4. PA spectroscopy spectra of poly (vinylidene fluoride) granulate in the II (a) modification and fibers in the ΐ(β) modification. Asterisks denote characteristic absorption bands of the 11(a) form.

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Vibrational Spectroscopy of Polymers

tooo

3Q00

2θδϋ 1500 WAVENUMBERS (a)

1000

500

> ϋ ζ in h

ζ

< < 3500

3000

2500

2000

1500

WAVENUMBER

10

(cm ) -1

(b) Figure

5. FTIR-PA

1000

(a) and FT-Raman (b) spectra of polyi^^phenylene terephthalamide) fibers.

3000

20'00

1500

1000

500

WAVENUMBERS Figure 6. FTIR-PA spectrum of a carbon-black-filled polycarbonate sheet.

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S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

were examined "as r e c e i v e d . " N o t w i t h s t a n d i n g t h e simplicity o f sample preparation f o r b o t h techniques, t h e F T I R - P A a n d F T - R a m a n spectra o f poly(vinylidene

fluoride)

granulate a n d fibers shown i n Figures 4 a n d 7,

respectively, clearly reflect absorption bands characteristic o f specific confor­ mational states o f order d u e to the differences i n the mechanical pretreatment o f the p o l y m e r d u r i n g the p r o d u c t i o n process. Whereas the granulate occurs p r i m a r i l y i n the T G T G conformation o f the 11(a) f o r m , the fibers have b e e n transformed largely to the all-trans conformation o f the Ι ( β ) modifica­ tion.

i500

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1000 500

WAVENUMBER

(cm )

WAVENUMBER

(cm" )

-1

1

Figure 7. FT-Raman spectra of poly (vinylidene fluoride) granulate in the 11(a) form and fibers in the l( β) modification.

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Vibrational Spectroscopy of Polymers

T h e p h e n o m e n o n o f saturation is demonstrated b y the strongly r e d u c e d intensities ( c o m p a r e d to a transmission spectrum) o f the v ( C = 0 ) a n d v ( C - N ) + δ ( Ν - Η ) absorptions o f the P A spectrum o f poly(p-phenylene terephthalamide) fibers ( F i g u r e 5a). T h e excellent quality o f the correspond­ i n g F T - R a m a n spectrum shown i n F i g u r e 5 b recommends F T - R a m a n spec­ troscopy as the m e t h o d o f choice f o r such samples where saturation effects dominate the P A spectrum. D e p e n d i n g o n the nature o f the filler, either F T I R - P A o r F T - R a m a n spectroscopy has advantages. I n the case o f carbonblack-filled polymers, F T - R a m a n spectroscopy usually fails to y i e l d useful spectra, whereas the excellent F T I R - P A spectrum obtained f r o m a sheet o f carbon-black-filled polycarbonate ( F i g u r e 6) emphasizes its value as a valu­ able alternative. O n the other h a n d , highly i n f r a r e d active filler materials such as glass fibers w i l l strongly overlap the actual p o l y m e r spectrum f r o m 1400 cm" to longer wavelengths, whereas they d o not significantly contribute to the F T - R a m a n spectrum ( 3 5 ) . 1

Depth-Profiling in Polymers by Attenuated-Total-Reflection FTIR Spectroscopy A l t h o u g h attenuated-total-reflection ( A T R ) spectroscopy is a well-established m e t h o d for the characterization o f p o l y m e r surfaces ( 3 , 4, 36), comparatively few available publications elucidate the detailed theoretical a n d practical b a c k g r o u n d f o r d e p t h profiling w i t h this technique ( 3 7 - 3 9 ) . T h e p r i n c i p l e o f A T R spectroscopy is based o n the p h e n o m e n o n o f total internal reflection. F o r the experiment the sample (refractive index n ) is brought into direct contact w i t h the surface o f a reflection element o f h i g h refractive index n (n > n ) . W h e n the angle o f incidence o f the light b e a m at the reflection e l e m e n t - s a m p l e interface exceeds the critical angle, total internal reflection takes place a n d the radiation slightly penetrates the optically rarer m e d i u m (4, 36). T h e penetration o f the radiation into the sample is usually o n the order o f a f e w micrometers, w h i c h is sufficient to constitute a short absorbing path. Therefore, total internal reflection w i l l b e attenuated i n the wavelength regions o f sample absorption a n d the r e c o r d e d spectrum w i l l b e very similar to the transmission spectrum. 2

l

2

l

T h e penetration d e p t h (d ) for w h i c h the electric field c o m p o n e n t decreased to 1 /e o f its value i n the reflection e l e m e n t - s a m p l e interface was derived theoretically b y H a r r i c k ( 3 6 ) : P

λ/η,

=

d v

7

1

2ττγ sin Θ 2

(%/%)

(2)

H e r e , Θ is the angle o f incidence, λ is the wavelength o f radiation i n v a c u u m , a n d n a n d n are the refractive indexes. T h i s equation d e m o n 1

2

56

S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN POLYMERS

/

Figure 8. Setup of the two-layer ATR measurements: surface layer of variable thickness, A; and detection layer, B.

strates the dependence o f penetration d e p t h o n the wavelength o f the radiation, the angle o f incidence a n d the refractive indexes o f the sample, a n d the reflection element. F o r the practical application o f the A T R m e t h o d i n p o l y m e r - p o l y m e r interdiffusion experiments, this theoretically d e r i v e d pene­ tration d e p t h is o f l i m i t e d value. W h a t is actually r e q u i r e d is a measure o f the d e p t h to w h i c h the composition o f the investigated p o l y m e r c a n b e reliably d e t e r m i n e d b y A T R spectroscopy u n d e r specified experimental conditions. T o this e n d , p o l y m e r films w i t h varying, definite thicknesses (surface layer) and a coating detection layer o f " i n f i n i t e " thickness were measured b y A T R - F T I R spectroscopy to determine the thickness o f the surface layer (later referred to as i n f o r m a t i o n d e p t h d^) at w h i c h characteristic absorption bands o f the detection layer are n o longer observable (40). T h e evaluation o f these systematic measurements should t h e n reveal the dependence o f the i n f o r m a ­ tion d e p t h o n the wavelength o f the i n c o m i n g radiation. T h e arrangement o f the surface a n d detection layers o n the A T R crystal is shown i n F i g u r e 8, a n d detailed results w i l l b e presented here w i t h reference to the system w i t h a polystyrene ( P S ) surface layer a n d a polyamide 12 detection layer. T h e reflection element was a K R S 5 parallelepiped w i t h a refractive index o f 2.39, a n angle o f incidence o f 4 5 °, a n d a total n u m b e r o f six reflections. T h e intensities o f the v ( N H ) , amide I, amide II, a n d δ ( Ν Η ) absorption bands o f the polyamide 12 detection layer w e r e d e t e r m i n e d as a function o f increasing thickness o f the polystyrene surface layer ( F i g u r e 9) and their n o r m a l i z e d intensities (Table I) plotted versus P S film thickness. Examples o f such plots are shown for the v ( N H ) a n d amide I bands i n F i g u r e 10. A linear wavelength dependence o f the i n f o r m a t i o n d e p t h d c a n b e d e r i v e d f r o m these data ( F i g u r e 11), a n d comparison o f the theoretically d e r i v e d penetration d e p t h d f o r polystyrene (1.59 refractive index) w i t h the experimentally d e t e r m i n e d i n f o r m a t i o n d e p t h d yields the relation (40) x

T

l

d

l

= 1.29 d

v

(3a)

2.

SlESLER

57

Vibrational Spectroscopy of Polymers

T h i s relation is very close to the relation d e t e r m i n e d f o r p o l y ( 2 , 6 - d i m e t h y l 1,4-phenylene ether) ( P P E ) w i t h polyamide 12 as the detection layer (40, 41),

(3b)

= 1.33 ά

ά

λ

Έ

a n d shows that a proportionality constant o f about 1.31 can b e used f o r any p o l y m e r system u n d e r the specified experimental conditions. I n more d e ­ tailed investigations this i n f o r m a t i o n d e p t h was used as the experimental basis for interdiffusion experiments

o f low-molecular weight polystyrene

into

p o l y ( 2 , 6 - d i m e t h y l - l , 4 - p h e n y l e n e ether) (41).

PS-FILM THICKNESS

3Ê00

3^00

3έϋϋ

3000

WAVENUMBERS

2§00

0

μπα

0.12

μm

0.31

μπι

0.64

μπι

6.78

μπη

2ΪθΟ

Figure 9. ATR spectra of polystyrene (PS) surface layers with different thickness and a polyamide 12 detection layer. Asterisks denote evaluated absorption hands. Continued on next page.

58

S T R U C T U R E - P R O P E R T Y RELATIONS IN POLYMERS

'l7Q0

lèSu

lèûO

ië5G

lèOÛ

TÎ5Ô

Roo

WflVENUMBERS Figure 9. Continued

Variable-Temperature FTIR Measurements and Hydrogen Bonding T h e role p l a y e d b y hydrogen bonds i n the structure a n d properties o f polymers has b e e n the subject o f numerous investigations ( 3 , 4,

42-44).

H y d r o g e n bonds are o f particular importance for the chemical, physical, a n d mechanical properties o f polymers that contain amide (polypeptides, proteins, polyamides), urethane (polyurethanes),

a n d hydroxyl [cellulose, poly(vinyl

alcohol), p o l y (acrylic acid)] functional groups. A l t h o u g h the energies o f hydrogen bonds are weak ( 2 0 - 5 0 k j / m o l ) i n comparison to covalent bonds ( o f the order o f 400 k j / m o l ) , this type o f molecular interaction is large enough to p r o d u c e appreciable frequency a n d

2.

59

Vibrational Spectroscopy of Polymers

SIESLER

Table I. Normalized Integral (») or Peak-Maximum (p) Absorbances of Selected Polyamide 12 Absorption Bands as a Function of Polystyrene Film Thickness (x and y are integration limits)

Sample Number

PS Film Thickness

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 a

c d

v(N-H)

0 0.05 0.07 0.12 0.31 0.63 0.64 1.09 1.33 1.35 1.49 1.53 1.79 2.13 2.31 2.43 2.45 6.78

χ= χ= x = v

m a x

1 0.49 0.51 0.47 0.10 0.04 0.09

— — — — — — — — — — —

v(C=0)

v(C-N) + δ(Ν-Η)

1 0.75 0.82 0.65 0.34 0.26 0.27 0.08 0.09 0.09 0.03 0.02 0.04

1 0.79 0.72 0.64 0.33 0.24 0.25 0.05 0.08 0.08 0.02 0.01 0.01

— — — — —

Ap/Ap δ(Ν-Η) max

1 0.77 0.84 0.84 0.53 0.49 0.53 0.37 0.42 0.42 0.37 0.32 0.28 0.30 0.23 0.28 0.23

— — — — —



3412 cm ~ y = 3160 cm , A4 ^'max = 24.28 1687 cm ~ y = 1610 cm A4 = 26.05 1590 cm - y = 1503 c m " A i = 27.29 = 720.6 c m " A p = 0.43 l

- 1

l

- 1

1

1

1

m a x

m a x

intensity changes i n the vibrational spectra. I n fact, the disturbances are so significant, that m i d - i n f r a r e d a n d R a m a n spectroscopy have b e c o m e one o f the most informative sources of criteria for the presence a n d strength hydrogen bonds ( 3 , 4, 44-46).

A n y variation of spectroscopic

of

parameters,

such as intensity, w a v e n u m b e r position, a n d b a n d shape, directly reflects the temperature

dependence

o f the vibrational behavior of the

p o l y m e r as a consequence of changes i n the inter- a n d

investigated

intramolecular

interactions. Unfortunately, only few vibrational spectroscopists

are

aware

that near-infrared spectroscopy offers a p o w e r f u l alternative to gain insight into these phenomena. T o demonstrate the potential of variable temperature measurements for the elucidation of hydrogen-bonding effects, the

results

obtained f r o m m i d - and near-infrared spectroscopic studies of thermoplastic polyamide 12 w i l l be outlined. I n polyamides a n d polyurethanes hydrogen b o n d i n g involves the p r o t o n donating group Ν H a n d the p r o t o n acceptor C = 0 .

M a n y o f the investiga­

tions so far reported deal w i t h the observed frequency shift and intensity increase of the v ( N H ) stretching vibration b a n d w h e n hydrogen b o n d i n g

60

S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

I.OQ

Ai/Ai

0.0 0.0

O.S

2.0

1.0

PS-FILM THICKNESS [ μ m3 (a)

Ai/Ai,

1.0

1.5

2.0

PS-FILM THICKNESS

2.5

3.0

3.5

Εμπι3

(b) Figure 10. Normalized integrated absorbanees (A/Ai ) of the v(NH) (a) and v(C = 0) (b) absorption bands of polyamide 12 versus polystyrene (PS) film thickness. The arrow marks the information depth d j . max

4.0

2.

SIESLER

61

Vibrational Spectroscopy of Polymers

10

WAVELENGTH λ c μ m ι Figure 11. Information depth dj of polystyrene as a function of wavelength (the detection layer is polyamide 12).

occurs (44-46). T h e frequency shift Δ ν ( Ν Η ) , i n particular, has b e e n corre­ lated w i t h various c h e m i c a l a n d physical properties o f the hydrogen b o n d (e.g., enthalpy o f formation, h y d r o g e n - b o n d distance) ( 3 , 4, 45, 46). Increas­ i n g hydrogen b o n d strength decreases the Ν · · · Ο distance, a n d this decrease is reflected b y an increase i n the shift between the v ( N H ) absorption frequency o f the associated a n d nonassociated N H functionalities. T h e v ( N H ) region o f the m i d - i n f r a r e d spectrum o f the investigated polyamide is shown i n F i g u r e 12. A c c o r d i n g to differential scanning calorimetric ( D S C ) measurements polyamide 12 melts at about 450 Κ a n d the following spectral changes o f the v ( N H ) b a n d are observed w i t h increasing temperature: • T h e intensity o f the v ( N H )

a s s o c i a t e d

b a n d decreases.

• T h e peak m a x i m u m o f the v ( N H )

a s s o c i a t e d

b a n d shifts toward

higher wavenumbers. • T h e half-bandwidth of the ν ( Ν Η )

ω 8 0 { ; ΐ α ί β < 1

b a n d increases consid­

erably. • A v(NH)

f r e e

b a n d appears at higher wavenumbers.

T h e w a v e n u m b e r shift a n d increase i n b a n d w i d t h o f the v ( N H ) b a n d at higher temperatures are the result o f a general weakening o f the hydrogen bonds a n d a concomitant broader distribution of the hydrogen b o n d energies. Unfortunately, the intensity of the v ( N H ) b a n d is very l o w i n the m i d - i n f r a r e d range and, additionally, at elevated temperatures the v ( N H ) absorptions o f the free a n d associated functionalities overlap. A total v ( N H ) absorbance procedure for the quantitative assessment o f hydrogen a s s o c i a t e d

f r e e

2

Figwre 22. Mid-infrared spectra of polyamide 12 in the v(NH) and v(CH ) temperature.

absorption region as a function of

50

w

Ο

S

δ

•υ w

>-d so ο

SO M I

to C Ο Η

H

cz>

to

2.

SlESLER

Vibrational Spectroscopy of Polymers

63

b o n d i n g i n polyamides and polyurethanes has b e e n p r o p o s e d b y Srichatrapimuk and C o o p e r ( 4 7 ) . H o w e v e r , for aliphatic polyamides, C o l e m a n et al. (48) have shown that w h e n the strong dependence of the absorption coefficient u p o n b a n d frequency (and, i n t u r n , the strength o f the hydrogen bond) is neglected, the p r o p o r t i o n of n o n b o n d e d N H groups at elevated temperatures d e r i v e d w i t h the foregoing procedure f r o m m i d - i n f r a r e d spectra i n the v ( N H ) region is too high. Inspection of F i g u r e 13 shows that near-infrared spectroscopy certainly offers an alternative b y evaluating the high-frequency w i n g of the 2 X v ( N H ) overtone absorption. F o r a quanti­ tative evaluation of n o n b o n d e d Ν H groups, however, the p h e n o m e n o n p o i n t e d out b y C o l e m a n et al. (48) as w e l l as the reversal o f the intensity ratio between the fundamentals of the free a n d associated Ν H groups and their first overtones must be taken into account (44). Additionally, contrary to m i d - i n f r a r e d spectroscopy, where the v ( O H ) absorption o f water is s u p e r i m ­ posed b y the dominating v ( N H ) b a n d o f the polyamide, the loss of water d u r i n g t h e r m a l treatment o f the p o l y m e r can readily be quantified b y the intensity decrease of the ν ( O H ) + δ ( Ο Η ) combination b a n d at about 5150 c m " . f r e e

1

Recent investigations (49; H . W . Siesler, u n p u b l i s h e d results) showed that variable-temperature F T I R spectroscopy w i t h p o l a r i z e d radiation can also be advantageously a p p l i e d to study the temperature-induced reorientational m o t i o n o f the mesogenic groups i n liquid-crystalline side-chain poly­ mers w i t h polyacrylate m a i n chains (50). T h e structure o f the investigated polymer, p o l y ( 1 -(6-(4 ' -cyanophenyl-4-benzyloxy)hexyloxycarbonyl)-ethylene), is shown i n F i g u r e 14 along w i t h the polarization spectra measured at r o o m temperature of a sample whose mesogenic groups were oriented i n the friction direction o f polyimide-coated a n d mechanically pretreated K R r windows. T h e molecular weight o f the p o l y m e r was 20,000 a n d the transition temperature f r o m the nematic to the isotropic phase was 133 °C (49). To study the relative orientational m o t i o n o f the mesogenic groups, the spacer a n d the m a i n chain as a f u n c t i o n of heating, the v ( C = N ) a n d ô ( C H ) absorption bands ( F i g u r e 14) were evaluated i n terms of their orientation functions (see e q 5). T h e sample was subjected to a p r o g r a m m e d heating o f l ° C / m i n and 64 scans were taken i n 1 - m i n intervals w i t h the polarization direction alternately parallel a n d perpendicular to the mechanical reference (friction) direction. D e p e n d i n g o n the t h e r m a l pretreatment, i n repeated measurements a strong reorientational behavior was observed between the glass transition (33 °C) and clearing point (133 °C) b e y o n d w h i c h the sample became isotropic. A l t h o u g h this behavior is not clearly understood, the orientation f u n c t i o n - t e m p e r a t u r e plot proves that, c o m p a r e d to the meso­ genic groups, the m a i n chains exhibit only relatively small orientational effects obviously as a consequence of small coupling. T h e spacers d e m o n ­ strate an intermediate behavior c o m p a r e d to the mesogenic groups a n d the m a i n chain. 2

Figure 13. Near-infrared spectra of polyamide 12 as a function of temperature. ta

S

δ

I

g

Su Ο M

*d

3d M I

ci

Η

α η

H ta

2

2.

SIESLER

Vibrational Spectroscopy of Polymers

65

Eheooptical FTIR Spectroscopy T h e mechanical properties o f p o l y m e r i c materials are of considerable i m p o r ­ tance to their engineering applications. A p a r t f r o m the chemical structure a n d the thermal history, molecular orientation has a major influence o n the mechanical properties of a polymer. T h e increased n e e d for more detailed data a n d a better understanding of the mechanisms involved i n p o l y m e r deformation has l e d to the search for n e w experimental techniques to characterize transient structural changes d u r i n g mechanical processes. W i t h the advent o f rapid-scanning F T I R spectroscopy, simultaneous vibrational spectroscopic a n d mechanical (so-called rheooptical) measurements d u r i n g the deformation o f polymers emerged. These rheooptical measurements were used as informative probes for the study o f deformation and relaxation p h e n o m e n a i n p o l y m e r films i n the late 1970s; since then they have b e e n applied to obtain data o n strain-induced crystallization and orientational a n d conformational changes d u r i n g mechanical treatment of a w i d e variety o f polymers (4, 46, 51). C o n t r a r y to the technique of time-resolved F T I R spectroscopy, w h i c h has i m p r o v e d t i m e resolution d o w n to the microsecond range due to o r d e r e d interferometric sampling techniques (52), the application of rheooptical F T I R spectroscopy is not restricted to the characterization of reversible structural changes caused b y small-amplitude oscillatory strains; therefore, irreversible p h e n o m e n a over large elongation and recovery scales may be studied (46, 51). T h e experimental p r i n c i p l e of rheooptical F T I R spectroscopy is illus­ trated i n F i g u r e 15. T h e technique is restricted to a film geometry of the sample and the specimen to be tested is uniaxially drawn a n d recovered i n the sample compartment o f the F T I R spectrometer. D u r i n g the mechanical treatment interferograms can be acquired i n small time intervals ( d o w n to 50 ms). U p o n c o m p l e t i o n of the experiment the interferograms are transformed to the corresponding spectra for further processing of the conventional data. T h e electromechanical apparatus constructed for the deformation a n d relax­ ation measurements is shown i n F i g u r e 16. F o r orientation measurements the polarization direction of the incident radiation is alternately adjusted parallel a n d perpendicular to the stretching direction b y a pneumatically rotatable w i r e - g r i d polarizer that is also controlled by the computer. T h e construction o f a heating c e l l as a closed, nitrogen-purged system allows the deformation and stress relaxation to be studied u n d e r controlled temperature conditions ( ± 0 . 5 K ) up to 523 K . Presently w e are testing the application of F T - R a m a n spectroscopy for rheooptical measurements. F o r this purpose, the stretching machine shown i n F i g u r e 16 is u t i l i z e d i n back-scattering geometry b y rotating the clamp mechanism for 90 ° w i t h the R a m a n b e a m i m p i n g i n g onto the sample through the front w i n d o w o f the stretching machine. T o improve the back-scattering

C/î

M

*d ο

δ

Η

tu

Μ

*d

Ο



I

ο

Η

ζΛ

Γ0

CD

φ

3obo

zobQ

1 ® iabo

if bo

120Q

WAVENUMBERS

i6bo

2

IGQO

υ yy •® 0) at higher elongations. T h e orientation function o f the v ( C - O - C ) absorption characterizes the soft segments that orient into the direction o f stretch u p o n elongation a n d disorient u p o n recovery. T h e contribution o f h a r d segments to the v ( C H ) absorption a n d the interfacial character o f the C = O functionality results i n deviations f r o m the orientation function behavior of the p u r e soft seg­ ments. T h e irreversible structural changes—elongations a n d orientations—are reflected b y the spectroscopic as w e l l as the mechanical data. - 1

2

e s t e r

a m i d e

a m i d e

2

e s t e r

T h e ability to m o n i t o r strain-induced crystallization i n the soft-segment phase o f the investigated p o l y m e r is demonstrated i n F i g u r e 21. F o r this purpose the integral structural absorbance ratio of the 9 9 7 - c m conformational-regularity b a n d of crystalline ofigotetrahydrofuran segments ( 5 6 ) a n d the 2 8 0 0 - c m thickness-reference b a n d has b e e n plotted along w i t h the intensity o f the reference b a n d versus strain. A p a r t f r o m thickness changes, the graph clearly demonstrates the appearance a n d disappearance o f straini n d u c e d crystallization as a function of l o a d i n g a n d unloading, respectively. - 1

- 1

Near-Infrared Spectroscopy A l t h o u g h the wavelength region of the near-infrared ( 1 0 , 0 0 0 - 4 0 0 0 c m or 1 0 0 0 - 2 5 0 0 n m ) has b e e n used over m a n y decades for the quantitative analysis o f compounds containing O H , N H , a n d C H functionalities (e.g., determination o f O H n u m b e r , water, protein, or residual d o u b l e - b o n d c o n ­ tent) (4, 57-59), it has never b e e n established as a w i d e s p r e a d analytical a n d physical tool comparable to m i d - i n f r a r e d spectroscopy. - 1

72

S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

I υ

I ζ

3600

3200 2800 WAVENUMBERS

2>i00

U ι

0

1800

i>ioo looo WAVENUMBERS

"èoo

Figure 17. Spectral assignment of the IR spectrum of the investigated poly (ether-block-amide).

I n the course o f the 1970s a n d 1980s however, t w o n e w developments initiated a renaissance of near IR-spectroscopy i n analytical chemistry. O n the one hand, chemometric data evaluation techniques i n combination w i t h d i f f u s e - r e f l e c t i o n measurements have o p e n e d u p the possibility o f nonde­ structive, rational multicomponent analysis o f solid samples. O n the other hand, the introduction of optical light fibers has contributed to an enormous instrumental expansion o f conventional near-IR spectroscopy i n terms o f remote control. F i b e r - o p t i c probes allow a separation o f the spectrometer a n d the sample measurement location over several h u n d r e d meters a n d greatly alleviate the analysis o f toxic or otherwise critical samples i n c l u d i n g process a n d reaction control. T h e basic difference between near- a n d m i d - i n f r a r e d ( 4 0 0 0 - 4 0 0 c m ) spectroscopy is attributed to the fact that the absorption bands observed i n the m i d - I R spectrum can (with f e w exceptions) be assigned to fundamental vibrations o f the investigated molecule, whereas the near-IR absorptions b e l o n g to overtone a n d c o m b i n a t i o n vibrations, p r i m a r i l y o f O H , N H , a n d C H functionalities. T h i s statement, however, may lead to an underestimation of the information content o f a near-IR spectrum because ( i n analogy to a m i d - I R spectrum) the near-IR spectrum also contains i n f o r m a t i o n o n the (1) temperature, (2) inter- a n d intramolecular interactions, (3) t h e r m a l a n d mechanical pretreatment, (4) ionic concentration (aqueous solutions), (5) viscosity/molar mass (polymers), (6) density, a n d (7) particle s i z e - f i b e r d i a m ­ eter ( i n the case o f d i f f u s e - r e f l e c t i o n spectra) o f the sample u n d e r investiga­ tion. - 1

T h e intensity o f an absorption b a n d decreases b y a factor o f about 1 0 - 1 0 0 i n going f r o m the fundamental to the first overtone, w h i c h necessi­ tates larger optical pathlengths for the near-IR spectral region (about 1 - 2 m m for u n d i l u t e d samples; u p to 100 m m for solutions). H o w e v e r , this leads

74

S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

to a considerable advantage i n sample h a n d l i n g c o m p a r e d to conventional m i d - I R spectroscopy

(4, 57). T h u s , Figures 2 2 a n d 2 3 demonstrate t h e

m o n i t o r i n g o f the U V - i n d u c e d polymerization o f a diacrylate b y m i d - a n d n e a r - I R spectroscopy, respectively. I n b o t h cases, information o n the amount o f residual double bonds i n the c u r e d resin c a n b e readily derived f r o m the decrease o f the 1 6 0 0 - c m

3500

- 1

p ( C = C ) absorption i n the m i d - I R region a n d the

3000

2600

WAVENUMBERS

WAVENUMBERS Figure 19. Polarization spectra recorded during elongation of the investigated poly (ether-block-amide) up to 300% strain.

2.

SIESLER

Vibrational Spectroscopy of Polymers

75

WAVENUMBERS Figure 19. Continued

2 v ( = C - H ) absorption at 1625 n m i n the n e a r - I R region w i t h the advantage o f a 200-fold increase i n thickness for the n e a r - I R sample a n d a concomitant ease o f sample h a n d l i n g . F u r t h e r m o r e , glass o r quartz, w h i c h are insensitive to water, may be used as w i n d o w materials i n the near-IR region. Instrumen­ tal advantages o f the light source a n d the detector allow near-IR spectra to be r e c o r d e d w i t h a signal-to-noise ratio signal-to-noise ratio

»

10,000 c o m p a r e d to the m i d - I R

< 10,000. T h i s observation supports the application o f

76

S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

strain



1

recover ,

A

A

α*

Α

δ

Α-ΕΡ

strain

A

A

, recover ,

a

strain

A

A

51

S -EH

V

ο ο "

°

v(NH) (CH ) 2

-A-V(C-O-C)

J

100

200

1 300

r-h 200 200

, 300

h 400

300

300

400

strain % () strain

recover .

strain

, recover .

strain

V c .2 I

§

n(C=0)

AMIDE

-A-V(C=0)

Ο ο

100

200

300

200 200

300

400

300

e s t e r

300

400

strain {%) Figure 20. Orientation function-strain plots of selected absorption bands corresponding to the mechanical treatment outlined in Figure 19.

2.

S IE s LE R

77

Vibrational Spectroscopy of Polymers

CO

strain

recover

strain

recover

• AAA

ι

100

200

300

~1——Γ 200 200

strain

*AAA

-δ le: ο L

A

CD

4300

400

300

300

400

strain (50 Figure 21. Monitoring of strain-induced crystallization in a poly (ether-blockamide) by rheooptical FTIR spectroscopy. chemometrie data evaluation techniques (60). Last, b u t n o t least, the materi­ als conventionally used as light fibers (glass, quartz) have a n attenuation m i n i m u m i n the near-infrared region (61, 62).

Near-Infrared Diffuse-Reflection Spectroscopy.

Near-infrared

spectroscopy has b e e n u s e d f o r almost t w o decades i n diffuse-reflection measurements f o r the analysis o f agricultural a n d f o o d products b y filter instruments (58, 5 9 ) . T e c h n o l o g i c a l progress has developed to a point w h e r e this technique c a n b e a p p l i e d w i t h scanning instruments i n the area o f c h e m i c a l a n d pharmaceutical m u l t i c o m p o n e n t analysis o f l i q u i d a n d solid formulations a n d i n p o l y m e r analysis. I n p r i n c i p l e , the m e t h o d belongs to the discipline o f chemometrics, w h i c h has b e e n recognized since the mid-1970s (63, 64). T h e purpose o f this discipline is to generate correlations between experimental data (e.g., absorption intensities i n the present case) a n d the c h e m i c a l composition o r physical properties o f the investigated samples b y mathematical a n d statistical procedures [e.g., multilinear wavelength regres­ sion ( M L W R ) , p r i n c i p a l component analysis ( P C A ) , partial least squares (PLS)]. T h e p r i n c i p l e o f the measurement p r o c e d u r e f o r quantitative analysis is based o n r e c o r d i n g the near-IR transmittance o r diffuse-refl ection spectra o f reference samples (the n u m b e r d e p e n d i n g o n the n u m b e r o f components o r parameters to b e determined) o f k n o w n composition. These spectra are

78

S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

«t000

3000

2000 1500 WAVENUMBERS

1000

500

polymer 8/um

h «*000

3000

2000 1500 WAVENUMBERS

1000

500

Figure 22. Mid-infrared spectra of the UV-induced polymerization of a diacrylate.

stored i n the c o m p u t e r o f the spectrometer, a n d the levels o f the constituents or the physical parameters are d e t e r m i n e d b y independent, conventional analytical o r physical methods. T h e n t h e set o f reference spectra a n d the independently d e t e r m i n e d values o f the parameters u n d e r investigation are used b y the selected statistical m e t h o d to b u i l d a calibration (57-60). U s e o f this existing standardization a n d t h e near-IR spectra enables the u n k n o w n samples to b e evaluated w i t h regard to the individual parameters o f interest. O n c e t h e calibration has b e e n p e r f o r m e d , t h e analysis t i m e r e q u i r e d f o r a n u n k n o w n sample is drastically r e d u c e d to a f e w minutes i n comparison to t h e several hours o r even days previously r e q u i r e d . P r o m i s i n g applications have b e e n reported ( 5 7 ) for the destruction-free analysis o f polymers o f w i d e l y varying m o r p h o l o g y i n c l u d i n g t h e determina­ t i o n o f characteristic c h e m i c a l a n d physical parameters o f synthetic fibers. T h e experimental results o n polyacrylonitrile fibers demonstrated here were obtained o n a near-IR spectrometer ( B r a n a n d L u e b b e 500) w i t h the fiber bundles m o u n t e d i n a sample c u p that is positioned u n d e r the integrating sphere. T h e measurement o f opaque solids is p e r f o r m e d i n diffuse reflection, whereas highly transparent solids, pastes, a n d liquids c a n b e measured w i t h the transflection m e t h o d , w h i c h is based o n a diffusely reflecting c e l l b o t t o m

2.

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79

Vibrational Spectroscopy of Polymers

ι H ; ιι;j' r

1

11 ΓΓ

monomer ' : ι · Γ. : ι : I

:uj: :Q:

-< :m: -GC:

o

2mm ±2

:

:CQ-

US

S.4 5^

polymer :

Ο - ζ -30.8-

3mm

:

•co-

6pQ4izt8fâQrz2OO0

2200.Γ

WAVELENGTH (nm) Figure 23. Near-infrared spectra of the U\ -induced polymerization of a diacrylate. 7

80

S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

that passes the radiation t h r o u g h t h e sample twice. T h e radiation directly reflected f r o m the gold-coated i n n e r surface o f the integrating sphere serves as a reference intensity ( F i g u r e 24). A r o u n d 100 s are r e q u i r e d to take a spectrum i n the 1 1 0 0 - 2 5 0 0 - n m wavelength range. T h e concentration p r o p o r ­ tional value o f l o g 1 /R is used as t h e ordinate scale:

logl/B = l / X > s

(6)

i C i

w h e r e R = I/I represents the intensity ratio o f light reflected b y the sample a n d t h e reference, respectively, s is the scattering coefficient, a are the absorptivities, a n d c are the concentrations o f the individual components. F r e q u e n t l y the first derivative o f l o g 1 /R is used to reduce the influence o f sample inhomogeneity ( 5 7 , 5 9 , 60). 0

{

{

T h e calibration was based o n t h e l o g 1 /R spectra o f about 70 reference samples. T h e spectrum o f such a reference sample is shown i n F i g u r e 25. I n T a b l e I I , the actual ( A ) a n d n e a r - I R - p r e d i c t e d ( P ) values a n d their residuals ( R ) f o r the parameters u n d e r investigation are shown f o r three test samples. These values demonstrate the potential o f this technique f o r rational c h e m i c a l a n d physical m u l t i c o m p o n e n t analysis.

SAMPLE REFERENCE MEASUREMENT

Figure 24. Simplified optical scheme of a scanning near-infrared diffusereflectance spectrometer.

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Vibrational Spectroscopy of Polymers

81

.700 +

.600

0.000 J

Figure

I 1200

1

1 1400

1

1 1600

1 ' 1 ' 1800 2000 WAVELENGTH (nm) 1

25. Near-infrared diffuse-reflectance spectra poly acrylonitnle fiber bundles.

1 ' 2200

of

1 2400

as-received

Table II. Actual (A) and Near-IR-Predicted (P) Values and Their Residuals R (P - A) of the Dimethylformamide (DMF) Solvent Residues and the Preparation, Shrinkage, and Strain of Polyacrylonitrile Fibers Measured as Fiber Bundles in Diffuse Reflection Sample

DMF (%)

Preparation (%)

Shrinkage (%)

Strain (%)

0.9342

0.2715

4.7389

22.9778

A

0.9200

0.2800

5.0000

22.8000

R

0.0142

-0.0085

-0.2611

0.1778

0.6661

0.2655

4.0705

20.4069

A

0.7000

0.2600

4.0000

21.0000

R

-0.0339

0.0055

0.0705

-0.5931

0.7107 0.7300

0.2797

A

0.2700

3.9485 3.9000

22.8066 23.0000

R

0.0193

0.0097

0.0485

-0.1934

IP

2P

3P

Near-Infrared Light-Fiber Spectroscopy. I n conventional transmission spectroscopy, the sample o f interest is measured i n the sample compartment o f the spectrometer, whereas the p r i n c i p l e o f fiber-optic spec­ troscopy is based o n the transfer o f fight f r o m the spectrometer v i a a suitable d e v i c e — t h e fight fiber—to the sample a n d back to the spectrometer after transmission of, o r reflection f r o m , t h e sample. S u c h light fibers usually consist o f quartz w i t h a length ranging u p to several h u n d r e d meters. Details

82

S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

POLYMER TEST SAMPLE (b) Figure 26. Optical scheme of a near-infrared light-fiber spectrometer with two applications of at-line monitoring: (a) At-line monitoring of process streams and (b) at-line monitoring of molecular orientation.

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83

Vibrational Spectroscopy of Polymers

ft i.25

1580 1600 1620 1640 1660 1680 1700 1720 1740 1760 1780 1880 1823

WAUELENGTHCNM] Figure 27. Near-infrared spectra of polystyrene-CCl solutions with different polystyrene concentrations measured on the flow. 4

o f light-fiber geometries, substrates, a n d optical properties are available i n the literature ( 6 1 , 62). T h e obvious advantage o f such a geometry is the ability to separate a n d vary the location o f measurement f r o m the spectrome­ ter w i t h i n the limits given b y the length o f the fight fiber. Various probes that can b e integrated into different reaction vessels or bypasses offer a m u l t i p l i c ­ ity o f remote sensing o n - a n d at-line process-control applications ( 6 5 ) . T h e optical scheme o f one o f the instruments used f o r o u r studies (the G u i d e d W a v e M 200 spectrometer) is shown i n F i g u r e 26. F i g u r e 26 also includes two applications o f transmission m o n i t o r i n g l i q u i d streams i n quartz tubes (a) a n d molecular orientation i n solid p o l y m e r test samples (b). I n b o t h cases t h e transmitted light is refocused into t h e return waveguide v i a a biconvex lens. T h e spectra obtained b y m o n i t o r i n g p o l y s t y r e n e - C C l solutions o f vari­ ous concentrations o n the flow i n a 1 9 - m m quartz tube are shown i n F i g u r e 27 ( 5 7 , 65). I n combination w i t h a near-IR polarizer ( G l a n - T h o m p s o n p r i s m ) the same optical configuration offers a very elegant approach for the characterization o f anisotropy i n p o l y m e r i c solids. T h i s anisotropy characteri­ zation is achieved b y evaluation o f the dichroic effects o f selected functionali­ ties measured w i t h light p o l a r i z e d parallel a n d perpendicular to t h e d r a w i n g direction o f the investigated p o l y m e r . F i g u r e 28 shows the near-IR polariza­ tion spectra o f a 2 6 0 % d r a w n polyamide 12 specimen (thickness 1.3 m m ) . T h i s spectra reflect significant dichroic effects o n t h e i n d i v i d u a l absorption bands ( 5 7 , 6 5 ) . C o m p a r i s o n o f the results d e r i v e d f r o m samples w i t h different draw ratios shows that the d i c h r o i c ratios obtained f r o m o n e overtone [e.g., 2 v ( C H ) ] c a n also b e transferred to t h e next overtone ( 3 v ( C H ) ] . N e a r - I R spectroscopy is u n i q u e for this purpose i n that i t offers a destruction-free investigation even o f thick specimens i n their original morphology. 4

2

2

84

S T R U C T U R E - P R O P E R T Y R E L A T I O N S IN P O L Y M E R S

ft 0,8026 Β 0.6548 0.5076 3 χ V(CH ) 0.3604

/

2

0.2131 0.0659 0.0813

ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—I

1200 1267 1333 1400 1467 1533 1600 1667 1733 1800 1867 1933 2000 HAUELEHGTHtNNl Figure 28. Near-infrared polarization spectra of a 260% drawn polyamide 12 test specimen measured with light polarized parallel (II ) and perpendicular ( ±) to the stretching direction.

Figure 29. Near-infrared light-fiber ATR sensor (see text). NA denotes the numerical aperture; n , n and n are the refractive indexes of air, the core, and the cladding, respectively. 0

l 5

2

2.

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Vibrational Spectroscopy of Polymers

85

A n application that shows promise is the modification o f a c o m m e r c i a l light fiber based o n a quartz core, a poly(dimethylsiloxane) cladding, a n d a polyamide coating ( F i g u r e 29) to act as a n A T R sensor i n the near-infrared region ( 6 6 ) . R e m o v a l o f the polyamide coating b y dissolution (over distances o f several meters) allows the r e m a i n i n g light fiber to b e w o u n d a r o u n d a T e f l o n holder a n d i m m e r s e d into the solution f o r analysis. This m e t h o d is based p r i n c i p a l l y o n the effect that the c o m p o u n d to b e d e t e r m i n e d c a n b e e n r i c h e d i n the p o l y (dime thylsiloxane) c l a d d i n g (with n o interference f r o m water, f o r example) a n d detected via total internal reflection o f the near-IR b e a m at the c o r e - c l a d d i n g interface. T o compensate f o r the absorptions o f the poly(dimethylsiloxane) cladding, a b a c k g r o u n d has to b e measured against air. A similar application has b e e n described f o r the m i d - i n f r a r e d region w i t h a polymer-coated internal reflection element ( 6 7 ) a n d a T e f l o n - c l a d d i n g fluoride glass optical fiber (68).

Acknowledgments T h e financial and instrumental support o f D e u t s c h e Forschungsgemeinschaft, R o n n , G e r m a n y , M i n i s t e r i u m f u r Wissenschaft u n d F o r s c h u n g des Landes N o r d r h e i n - W e s t f a l e n , Dusseldorf, G e r m a n y , F o n d s d e r C h e m i s c h e n Indus­ trie, F r a n k f u r t , G e r m a n y , H i i l s A G , M a r l , G e r m a n y , Bayer A G , D o r m a g e n , G e r m a n y , a n d B r a n a n d L u e b b e G m b H , Norderstedt, G e r m a n y , are grate­ fully acknowledged. T h e author also thanks S. D e k i e r t , B . Feldhâuser, U . Becker, P . W u , a n d I. Grose for experimental assistance.

References 1. Geick, R. In Topics in Current Chemistry; Springer: Berlin, Germany, 1975; Vol. 58, p 73. 2. Griffiths, P. R.; deHaseth, J. A. Fourier-Transform Infrared Spectroscopy; Chem­ ical Analysis Series 83; Wiley: New York, 1986. 3. Koenig, J. L. Adv. Polym. Sci. 1983, 54, 87. 4. Siesler, H . W.; Holland-Moritz, K. Infrared and Raman Spectroscopy of Polymers; Dekker: New York, 1980. 5. Gilson, T. R.; Hendra, P. J. Laser-Raman Spectroscopy; Wiley: New York, 1970. 6. Koenig, J. L. Appl. Spectrosc. Rev. 1971, 4(2), 233. 7. Cutler, D. J.; Hendra, P. J.; Fraser, G. In Developments in Polymer Characterization; Dawkins, J. V., Ed.; Applied Science Publishers: London, England, 1980; V o l . 2, p 71. 8. Hirschfeld, T.; Chase, B. Appl. Spectrosc. 1986, 40, 133. 9. Zimba, C. G.; Hallmark, V. M.; Swalen, J. D.; Rabolt, J. F. Appl. Spectrosc. 1987, 41, 721. 10. Hendra, P. J., Ed. Spectrochim. Acta 1990, 46A(2), 121. 11. Schrader, B.; Hoffmann, Α.; Simon, Α.; Sawatzki, J. Vibrational Spectrosc. 1991, 1, 239. 12. Hendra, P. J.; Jones, C.; Warnes, G. Fourier Transform Raman Spectroscopy; Ellis Horwood: Chichester, England, 1991. 13. Sawatzki, J.; Simon, A. In XXIIth International Conference on Raman Spec­-

86

STRUCTURE-PROPERTY RELATIONS IN POLYMERS

troscopy, August 13-17, 1990, Columbia, South Carolina; Durig, J. R.; Sullivan, J. F., Eds.; Wiley: Chichester, England, 1990. 14. Plueddemann, E. P. Silane Coupling Agents; Plenum: New York, 1983. 15. Ishida, H.; Koenig, J. L. Polym. Eng. Sci. 1978, 18, 128. 16. Graf, T. R.; Koenig, J. L.; Ishida, H . Anal. Chem. 1984, 56, 773. 17. Davis, J. Α.; Sood, A. Makromol. Chem. 1985, 186, 1631. 18. Siesler, H . W. Mikrochim. Acta (Wien) 1988, I, 319. 19. Bell, A G. Philos. Mag. 1881, 11, 510. 20. Rosencwaig, A. Opt. Commun. 1973, 7, 305. 21. Rosencwaig, A. Photoacoustics and Photoacoustic Spectroscopy; Wiley: New York, 1980. 22. Pao, Y.-H., Ed. Optoacoustic Spectroscopy and Detection; Academic: Orlando, FL, 1977. 23. Somoano, R. B. Angew. Chem. 1978, 90, 250. 24. Hunter, T. F.; Turtle, P. C. In Advances in IR and Raman Spectroscopy; Clark, R. J. H.; Hester, R. E., Eds.; Heyden: London, England, 1980. 25. Coufal, H.; McClelland, J. F. J. Mol. Struct. 1988, 173, 129. 26. Graham, J. Α.; Grim, W. M., III; Fateley, W. G. In FTIR Spectroscopy—Applica­ tions to Chemical Systems; Ferraro, J. R.; Basile, L. J., Eds.; Academic: Orlando, FL, 1985; Vol. 4,p345. 27. Vidrine, D. W. Appl. Spectrosc. 1980, 34, 314. 28. Rockley, M . G. Appl. Spectrosc. 1980, 34, 405. 29. Yang, C. Q.; Fateley, W. G. Anal. Chim. Acta 1987, 194, 303. 30. Urban, M . W. J. Coat. Technol. 1987, 59, 29. 31. Adams, M . J.; King, Α. Α.; Kirkbright, G. F. Analyst 1976, 101, 73. 32. McClelland, J. F.; Kniseley, R. N. Appl. Opt. 1976, 13, 2658. 33. Rosencwaig, Α.; Gersho, A. Science 1975, 19, 556. 34. Rosencwaig, Α.; Gersho, A. J. Appl. Phys. 1976, 47, 64. 35. Grose, R. I.; Hvilsted, S.; Siesler, H . W. Makromol. Chem., Makromol. Symp. 1991, 52, 175. 36. Harrick, N . J. Internal Reflection Spectroscopy; Interscience: New York, 1980. 37. Gidaly, G.; Kellner, R. Fresenius Z. Anal. Chem. 1980, 302, 257. 38. Ohta, K.; Iwamoto, R. Appl. Spectrosc. 1985, 39, 418. 39. Blackwell, C. S.; Degen, P. J.; Osterholtz, F. D. Appl. Spectrosc. 1978, 32, 480. 40. Becker, U. M.Sc. Thesis, University of Essen, Essen, Germany, 1988. 41. Machate, Ch., Ph.D. Thesis, University of Münster, Münster, Germany, 1989. 42. Painter, P. C.; Coleman, M . M . ; Koenig, J. L. The Theory of Vibrational Spectroscopy and Its Applications to Polymeric Materials; Wiley-Interscience: New York, 1982. 43. The Hydrogen Bond; Schuster, P.; Zundel, G.; Sandorfy, C., Eds.; North-Holland: New York, 1976. 44. Vinogradov, S. N.; Linnell, R. H . Hydrogen Bonding; Van-Nostrand Reinhold: New York, 1972. 45. Murthy, A. S. N.; Rao, C. N . R. Appl. Spectrosc. Rev. 1968, 2, 69. 46. Siesler, H . W. Adv. Polym. Sci. 1984, 65, 1. 47. Srichatrapimuk, V. W.; Cooper, S. L. J. Macromol. Sci. Phys. 1978, B15, 267. 48. Skrovanek, D. J.; Painter, P. C.; Coleman, M . M . Macromolecules 1985, 18, 299 and 1676. 49. Bürkle, K.-R. Ph.D. Thesis, University of Ulm, Ulm, Germany, 1987. 50. Zentel, R.; Benalia, M . Makromol. Chem. 1987, 188, 665. 51. Siesler, H . W. Makromol. Chem., Makromol. Symp. 1992, 53, 89. 52. Noda, I. Appl. Spectrosc. 1990, 44(4), 550.

2.

SIESLER

Vibrational Spectroscopy of Polymers

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53. Ishihara, H.; Kimura, I.; Saito, Κ.; Ono, H . J. Macromol. Sci. Phys. 1974, B10, 591. 54. Lohmar, J.; Meyer, K.; Goldbach, G. Makromol. Chem. 1988, 189, 2053. 55. Bonart, R.; Hoffmann, K. Colloid Polym. Sci. 1982, 260, 268. 56. Tadokoro, H.; Kobayashi, M . In Polymer Spectroscopy; Hummel, D. O., Ed.; Verlag Chemie: Weinheim, Germany, 1974; p. 1. 57. Siesler, H . W. Makromol. Chem., Makromol. Symp. 1991, 52, 113. 58. Weyer, L. G. Appl. Spectrosc. Rev. 1985, 21, 1. 59. Osborne, B. G.; Fearn, T. Near Infrared Spectroscopy in Food Analysis; Wiley: New York, 1986. 60. Hirschfeld, T.; Stark, E. In Analysis of Food and Beverages; Charamboulos, G., Ed.; Academic: Orlando, F L , 1984; p 505. 61. Herbrechtsmeier, P. Chem. Ing. Tech. 1987, 59, 637. 62. Frank, W. Fernmelde-Ing. 1990, 44(3), 1. 63. Sharaf, Μ. Α.; Illman, D. L.; Kowalski, B. R. Chemometrics; Wiley-Interscience: New York, 1986. 64. Martens, H.; Naes, T. Multivariate Calibration; Wiley: Chichester, England, 1989. 65. Feldhäuser, Β. M.Sc. Thesis, University of Essen, Essen, Germany, 1988. 66. Bürck, J.; Conzen, J.-P.; Ache, H.-J. Fresenius J. Anal. Chem. 1992, 342, 394. 67. Heinrich, P.; Wyzgol, R.; Schrader, B.; Hatzilazaru, Α.; Lübbers, D. W. Appl. Spectrosc. 1990, 44(10), 1641. 68. Ruddy, V.; McCabe, S. Appl. Spectrosc. 1990, 44(9), 1461. RECEIVED for review May 14, 1991. ACCEPTED revised manuscript September 22, 1992.