Anal. Chem. 1995, 67, 97R-126R
Analysis of Synthetic Polymers and Rubbers Charles 0. Smith,* Patrick B. Smith, Andrew J. Pasztor, Jr., Marianne L. McKelvy, David M. Meunier, and Stephen W. Froelicher Analytical Sciences Laboratory, Dow Chemical U.SA., 1897 Building, Midland, Michigan 48667 Review Contents
Gas Chromatography Pyrolysis Techniques Liquid Chromatography Mass Spectrometry Nuclear Magnetic Resonance Spectroscopy Thermal Analysis Infrared and Raman Spectroscopy
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This paper reviews techniques for the characterization and analysis of rubbers and synthetic polymers, copolymers, and blends. Chromatographic techniques such as gas chromatography, inverse gas chromatography, pyrolysis gas chromatography, and liquid chromatography including size exclusion chromatography are included in this review. Also included are references to mass spectrometry, spectroscopictechniques including infrared, Raman, and nuclear magnetic resonance, and thermal techniques such as thermogravimetric analysis and differential scanning calorimetry. Applications include structure determination, separation and quantitation of residual monomers and additives, determination of molecular weight, and study of degradation mechanisms and other thermal properties of synthetic polymers and rubbers. A majority of the cited references were obtained from literature searches and volumes of Chemical Abstracts or CA Selects published between October 1992 and October 1994. For the most part, this review contains references to journals published in English and readily available in the United States. GAS CHROMATOGRAPHY A capillary gas chromatographic method was validated for topanol A and topanol 0 antioxidants at concentrations of a p proximately 250 ppm in 11-bromoundecyl methacrylate and 50 ppm in methyl methacrylate. The analysis was performed using a temperature-programmed 10 m x 0.53 mm i.d. HP-1 capillary column with a camer gas flow rate of 16.5 mL/min (AI). Ethyl acetate extraction followed by gas chromatography with electron capture detection was used for routine simultaneous determination of epichlorohydrin,3-chloro-1,2-propanediol, and 1,3dichloro-2-propanol in aqueous solutions of a poly(amido amine) epichlorohydrin resin. These impurities were detected at detection limits in the micrograms per gram range 642). A review presented examples of the application of gas chromatography and gas chromatography/mass spectrometry (GC/ MS) by the paint and coatings industry. The review described techniques and references for monitoring of raw material quality, resolving manufacturing problems, and identifying the polymers and other components of coatings (A3). Mineral water samples, stored in polyethylene-lined aluminum/ cardboard packages, were incubated at 40 "C, and then volatiles in the mineral water were analyzed by sni€iing the effluent from a gas chromatographic column. The effluent was sensorially 0003-2700/95/0367-0097$15 5010 0 1995 American Chemical Society
evaluated for the intensity of descriptors such as synthetic, sickly, musty, metallic, or dry. Components detected by sniffing were subsequently identified by gas chromatography/mass spectrometry as aromatic hydrocarbons and carbonyls (A4). Styrene and styrene dimers (at concentrations of 13 and 43 mg/kg, respectively) were the major components among the 20 compounds identified by G U M S in polystyrene used for milk packaging. The detection limit for styrene monomer by this equilibrated headspace method was 0.29 mg/kg. In a related procedure to determine styrene and the dimer in milk, acetone was used to precipitate proteins and extract fat and the residues from the packaging material. Using direct injection of these extracts for GC analysis, detection limits were 0.16 mg/kg for styrene and 0.28 mg/kg for the dimer (A5). Sensory evaluation panels and gas chromatography were used to characterize odors from commercial polyethylene. Tenax-GC collection tubes were used to trap the odor-active volatiles at ambient temperature (A@. Because of their relatively low viscosity and good curing properties, Mannich base products are frequently selected as curing agents for epoxy resins. A direct gas chromatographic method with flame ionization detection was described for the determination of residual levels of phenol, formaldehyde, and benzyl alcohol in Mannich formulations used as curing agents. For toxicological reasons, this sensitive method, linear over a broad range of concentrations, was needed to monitor concentrations of phenol, which is subject to legal restrictions (A7). Hightemperature capillary gas chromatography was also used to separate novolac phenolic and epoxy novolac oligoiners (AS). Methyl methacrylate monomer evolved during aging of poly(methyl methacrylate) at different temperatures was determined by gas chromatography and polarography. An exponential relationship existed between the yield of monomer and the aging temperature (AS). A modified headspace gas chromatographic method was described for the determination of free methyl methacrylate monomer in contact lenses regardless of their method of production. This method allowed supervision of the quality of a lens of unknown origin within 15 min, and the test was used to evaluate production tests of new polymerization initiators ( A l O ) . Epoxidued soybean oil, a common additive in polymers such as poly(viny1chloride) (PVC), was converted into fatty acid esters with tetramethylammonium hydroxide, and these derivatives were analyzed by capillary gas chromatography using flame ionization detection. For PVC, the epoxidued soybean oil was extracted with toluene, derivatized, and analyzed. A short capillary column was used to separate the methyl esters of mono-, di-, and triepoxyoctadecanoic acid (All). Multidimensional techniques of heartatting, cryotrapping,and back-flushing were used to develop a capillary-based alternative to the packed-column techniques to determine residual vinyl chloride monomer in PVC. This capillary-based method resolved Analytical Chemistry, Vol. 67, No. 12, June 15, 1995 97R
some of the problems associated with the accuracy and reproducibility required for the ultratrace determination of this suspected carcinogen (412). Element-specific chromatograms using an atomic emission detector (AED) provided information on the types of additives in a variety of polymer extracts. The high resolution of capillary gas chromatography and the selectivity and sensitivity of the AED complemented mass spectrometry and infrared for the characterization of additive mixtures in supercritical fluid extracts from a rubber sample (413). Headspace sampling and gas chromatography were used to quantitatively follow the thermal oxidation of a low molecular weight hydroxy-terminated polybutadiene. Rate studies using this simple, efficient technique revealed an induction period for the oxidation followed by self-catalyzed oxidation. The rate for this latter step was quickly controlled by the diffusion of oxygen into the polymer (414). Gas chromatography was used to study the kinetics of evolution of volatiles from polypropylene at 70 "C. Correlation chromatography and trapping volatiles on Tenax sorbents or activated charcoal were used to improve the detector signal. A series of direct injections of the polymer headspace followed by gas chromatography was used as a reference study of the kinetics of gas evolution. Data from the trapping studies differed from results from the direct injections and the correlation chromatographic studies, which were in good agreement (415). A polymer, not readily identified by other techniques because of interference from additives, was identified using a direct dynamic headspace device designed for use with GC/MS. This device was designed to identify compounds with boiling points too low for analysis by conventional GC analysis (416). Inverse gas chromatography (IGC) continued to be a useful technique to determine physicochemical properties of pure polymers, polymer solutions, and polymer blends. Thermal transitions, polymer solubility parameters, polymer/solvent and polymer/polymer interaction parameters were measured using the polyfiydroxy ether of Bisphenol A), solutions of this polymer, and blends with other polymers (417). Two equations were derived to analyze data from capillary IGC experiments to determine solubility and d ~ s i v i t yfor polymer/solvent systems 6418).
Inverse GC was used to construct adsorption isotherms for n-hexane, n-heptane, n-octane, and n-nonane on polystyrene at 30 "C. Isotherms were also developed for n-heptane at 40, 50, and 60 "C. Partition coefficients calculated for these alkanes increased for increasing chain length of the probe compound and decreased with increasing temperature (419). Inverse GC was also used with some of the same solvents to determine weight fraction activity coefficients and Flory-Huggins parameters for polystyrene
WO). Other authors used IGC to develop phase diagrams for systems containing polystyrene with high carbon number alkanes (up to n-pentatricontane) at 190-250 "C. The Gibbs free energy of mixing (AC,J was calculated for the polystyrene-alkane systems by assuming the Flory-Huggins parameter was independent of composition W1).The same co-workers reported using IGC to determine diffusion coefficients of caprolactam in nylon 6 using a capillary column at 250-280 "C. Activity coefficients at infinite dilution were also determined and compared with values obtained using packed columns (A22). One of these same authors reported 98R
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measurement of activity and diffusion coefficients of several solvents in polystyrene using a capillary column at temperatures between 110 and 170 "C (A23). The retention diagram of poly@-chlorostyrene) for tert-butyl acetate, obtained using IGC, showed a low critical solution temperature, indicating that the polymer solubility in this solvent decreased with temperature. The experiments also allowed calculation of the weight fraction activity coefficient, the FloryHuggins interaction parameter at infinite dilution, and the effective exchange interaction parameter for this polymer/solvent system (A24). Some of the same co-workers determined several thermodynamic interactions for poly(pch1orostyrene) with n-pentane, n-hexane, n-heptane, benzene, toluene, n-propylbenzene, and isopropylbenzene at 150-170 "C. Molar enthalpy of sorption, the partial molar heat of mixing at infinite dilution, and the solubility parameter were also determined for this polymer 0. Thermodynamic interaction parameters of polystyrene and polybutadiene were determined with 15 probes of different polarities at temperatures from 155 to 185 "C. Polymer/polymer interaction parameters were also measured by using five different polystyrene-polybutadiene blend compositions. These IGC experiments indicated a definite probe dependence (A26). Inverse GC was used to investigate surface and interaction properties for styrene-4vinylpyridine diblock copolymers. When this copolymer was adsorbed on an acidic Chromosorb support, the more basic vinylpyridine block was preferentially oriented to the substrate. The air interphase was enriched in polystyrene (A27). Specific retention volumes of several probe compounds in poly(4hydroxystyrene), poly(viny1 acetate), and four blends of these homopolymers were used to determine the thermodynamic interaction between the polymers. An apparent probe dependence seemed to be related to the strength of the probe interaction with the individual homopolymers 0228). A methacrylic acid-styrene diblock copolymer adsorbed on particulates with varying acid/base interaction potentials was studied by IGC. The acid/base interactions between the substrate and the polymer resulted in selective adsorption of the copolymer moieties (A29). Acid/base interactions were also estimated by exposing the surface of polystyrene to acidic and alkaline vapors and calculating the interaction parameter (A30). Dispersive and acid/base properties of the surfaces of two cross-linked poly(dimethacry1ates) were also examined using inverse gas chromatography. Parameters defining the ability of the surfaces to accept or donate electrons were sufficiently sensitive to describe surface changes that occurred during thermal treatment and variations in the structure of the ester groups (431). One of these co-workers also used IGC to determine binary parameters to aid in the characterization of surfactants based on oxyethylene derivatives of 1-hexadecanol (A32). Transition temperatures and interaction parameters from inverse GC experiments with poly(ethy1ene oxide), poly(ethy1 methacrylate), or poly(ethy1 methacrylate-co-methacrylic acid) indicated compatibility of poly(ethy1 methacrylate) with poly(ethylene oxide). The copolymer, however, was incompatible with poly(ethy1ene oxide) because of interactions between the acid groups in the copolymer and the ether moieties of poly(ethy1ene oxide) (433). Inverse gas chromatographic columns were prepared with a blend of poly(ethy1ene oxide), poly(methy1 methacrylate), and a pulverized porous silica gel. Changes in the retention diagrams
gave information on the interaction between the polymer blend and the silica gel, which incorporated both polymers into its pores 6434) * Characteristic retention data and peak shape changes were observed with inverse GC of olefinic stationary phases impregnated with silica gel or carbon black. Air was used as the carrier gas. The experimental system was designed as a model for the degradation of reinforced vulcanizates (A35). Inverse gas chromatographic experiments with a styrenebutadiene rubber stationary phase were conducted at temperatures above and below the glass transition temperature (Tg) with flow rates up to 60 mL/min. Retention volumes decreased with rising gas flow at temperatures above Tgr and equilibrium values were obtained at high flow rates. Because these equilibrium values were related to surface interactions, this IGC technique was useful for studying the surface character of polymers above Tg(A36'). The same co-workers also used IGC to study dispersive surface energies and acid/base interactions for a styrene/maleic anhydride copolymer over a broad range of temperatures (A37). The interactions between filler particles and polymer surfaces in paints and other particulatefilled composite formulationswere measured by determining the retention behavior of organic solvent molecules through columns packed with polymer or filler particles. This review of the IGC technique, with 51 references, included intermolecular interaction and gas chromatographic theory. Equations were also presented for calculation of free energy, surface energy for polymer and filler particles, and entropy of adsorption of the polymers on the filler particles (A38, A39). Other workers reported using inverse GC to characterize the acid/base interactions of the components of paint formulations including polymers, pigments, additives, and solvents. The technique gave good results for the determination of Tg, the weight fraction activity coefficient at infinite dilution, and the heat of interaction for selected solvents (A40). Another study reviewed the use of IGC to characterize fillers such as CaC03 and talc that are used in paints and coatings. These data demonstrated that steric hindrances affected the adsorption of probe molecules on lamellar solids like talc (A41). Other workers used IGC to measure speciiic retention volumes and derive interaction parameters for nine different polymers and 43 solvents at six different temperatures in the range of 60-110 "C (A42). The thermodynamic miscibility behavior of polycarbonates based on 4,4'-isopropylidenebisphenol and 4,4'-cyclohexylidenebisphenol units was examined by inverse gas chromatography.The speciiic retention volumes were measured using a variety of solvents at temperatures above the glass transition temperatures of these polymers (A43). Several workers reexamined the problem of solvent iduence on the determination of polymer/polymer interaction parameters by inverse gas chromatography (A44). Some of the same coworkers used IGC to measure polymer/polymer interaction parameters for poly(viny1 chloride)-poly(ethylene oxide) blends (A45).
Other workers used the technique to study poly(viny1 methyl ether) -poly(vinyl ester) blends (A46). The hydrogenated monomers of the poly(viny1 esters) were used as the analog probes and the poly(viny1methyl ether) was used as the stationaryphase. This study indicated that poly(viny1 methyl ether) was miscible with poly(viny1butyrate) and poly(viny1propionate) but it was not miscible with poly(viny1 acetate).
An acrylonitrile-methyl acrylate-sodium 2-acrylamido-2-methylpropane-1-sulfonate copolymer was coated on a Chromosorb W substrate. A column packed with this material was conditioned at four temperatures under a flow of nitrogen. Plots of retention volume versus the inverted temperature were prepared for probe solvents including NJ-dimethylformamide, pyridine, 1-propanol, and pxylene (A47). Swelling measurements, stress/strain mechanical analysis, and inverse gas chromatography were used to determine the crosslink density of three poly(dimethylsi1oxane) samples. Results were in good agreement, and the IGC experiments also allowed calculation of interaction parameters for the linear and cross-linked polymers (448). Poly(viny1 chloride) was also studied by IGC. The technique was used to determine the weight fraction activity coefficient at infinite dilution and the interaction parameter for various PVC probe systems (449) while other workers measured glass transition temperatures and the molar heat of adsorption of selected probe molecules. The glass transition temperature was almost independent of the type of probe molecule (A50). Polymer/solvent interaction data were also generated for polyisobutylene with four chemical families of solvents with increasing backbone length 0154, and IGC was used to study the compatibility of polyurethane foam with liquids at various temperatures. In the latter case, the results were used to predict the noninteractive barrier properties of a polyurethane foam against liquids with different polarity 0152). The polymer/ polymer interaction parameters calculated from IGC data and results from differential scanning calorimetry showed that acrylic acid-styrene copolymers and poly(isobuty1 methacrylate) were immiscible (A53). The curing of unmodified and diol-modifiedepoxy resins based on the diglycidyl ether of Bisphenol A was also studied by IGC. The activation energy of the cross-linking reaction and diffusion coefficients for solvent injected into curing and cured epoxy resins were obtained by varying gas chromatographic conditions (A54). The technique was also used to calculate polymer/polymer interaction parameters and the interaction energy densities for blends of poly(6caprolactone) with poly(hydr0xy ether of Bispheno1 A). Parameters were evaluated at temperatures between 130 and 160 'C for three different blend compositions (A55). Some of the same workers used IGC to investigate a blend of poly(hydroxy ether of Bisphenol A) and poly(viny1 methyl ether). Interaction parameters were calculated and specific retention volumes were measured for probes in both pure and mixed stationary phases (A56). Use of IGC below Tgto determine adsorption properties at the surface of glassy polymers such as polystyrene and poly(methyl methacrylate) often results in broad peaks. Comparing diffusion coefficients with IGC data, however, indicated that equilibrium diffusion through these polymers was not responsible for the broadened peaks. Flow rate changes also had no effect on retention times (A57). Inverse GC was also used to determine solubility parameters and components correspondingto polar, dispersive, and hydrogenbonding interactions of 19 diamino oligoethers. This study included examination of the relationship between solubility and polarity parameters and the influence of structure on solubility parameters (A58). Analytical Chemistry, Vol. 67, No. 12, June 15, 1995
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Transition temperatures of a mainchain biphenyl-based organic polyester liquid crystal were determined using IGC. These transition temperatures agreed with values determined by other techniques, and data were available on a range of temperature related properties of these liquid crystals (359). Finally, the inverse GC technique was used to characterize the interaction of a polyether-polyurethane with 17 solvents of different polarities. The specific retention volumes measured for each probe at 100-150 "C were used to calculate properties at infinite dilution and other thermodynamic parameters @SO). PYROLYSIS TECHNIQUES Pyrolysis gas chromatography (Py-GC) and gas chromatography/mass spectrometry (Py-GUMS) continued to be used to characterize the structure of copolymers, polymer blends, geopolymers, biological materials, and archaeological or historical objects. Only applications to polymers, blends, and rubbers are included in this review. Peak areas for styrene trimer and relative peak ratios for the trimer/dimer peaks in pyrograms of polystyrene were used to evaluate an improved Curie point pyrolyzer (BI). The same workers also developed a multichannel autosampler for Curie point pyrolysis with capillary gas chromatography. This unit was evaluated using an ABS copolymer and thermally labile samples that could be analyzed without thermal degradation or reaction during the waiting period before pyrolysis (B2). Subsequent modification of this multichannel pyrolyzer included a shorter transfer line between the pyrolyzer and the gas chromatograph. This modifcation eliminated dead volume and permitted transfer line operation at 300 "C, resulting in improved yields of highboiling, highly polar, and thermally labile pyrolysis products (B3). In another instrument development, a simple laser pyrolyzer with a lower volume pyrolysis chamber was used to study high molecular weight polymers by Py-GC and Py-GUMS (B4).An infrared instrument was also developed to analyze volatile products from solid samples including polymers and soil samples. The samples were heated with an infrared radiation source in an optically focused system that allowed collection of the pyrolysis products in sorbent-filled tubes. These collected pyrolyzates were subsequently desorbed and examined by G U M S (B5). Reference materials or standards were introduced into a capillary gas chromatographic system during pyrolysis of polymer samples. The reference material or standard was adsorbed on a Tenax porous polymer support that was placed into a second 358 "C Curie point wire. This material was subsequently thermally desorbed during Curie point pyrolysis of the polymer sample (B9. Products from the thermal degradation of poly(styrene disulfide) (PSD) and poly(styrene tetrasulfide) (PST) were identified using pyrolysis mass spectrometry and flash pyrolysis-GC/MS. Pyrolysis products containing sulfur, styrene, cyclic styrene sulfides, and diphenyldithianes were observed from the PSD. Flash pyrolysis-GUMS, however, yielded only styrene, sulfur, one cyclic styrene sulfide, and diphenylthiophen isomers. These latter compounds were absent from the PST pyrograms (B7). Poly(phenylene sulfide) degradation was also studied by flash pyrolysis-GC/MS. Cyclic tetramer and linear dimers and trimers from random scission of the polymer followed by cyclization were the major products from pyrolysis at 550 "C (B8). Pyrolysis-GC was used to determine the end groups in polystyrene prepared by anionic polymerization using a n-butyllOOR
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lithium initiator. Because the peaks associated with end groups decreased with increasing polymer molecular weight, the numberaverage molecular weight was estimated by comparing the intensities of these end group peaks relative to the total intensity for all peaks from pyrolysis of samples with different molecular weights (B9). In a related study, methacrylol end groups of polystyrene were determined by stepwise Py-GC utilizing a twostage pyrolyzer in combination with on-line methylation (BIO). Analytical-scale pyrolysis was used to model the hot-wire cutting of expanded polystyrene. The gas chromatograms were not affected by the presence of flame retardants, and pyrolysis products were similar in air or an inert gas. The heating temperature was the major factor affecting the yield and distribution of pyrolysis products ( B I I ) . Gas chromatography/mass spectrometry was also used to identify the volatile pyrolyzates from the large-scale pyrolysis of styrene-acrylonitrile and ABS copolymers (BIZ). Neutral sizing agents such as alkylketene dimers and alkenylsuccinic anhydride were determined in paper by pyrolysis gas chromatography. Peaks were observed for the intact alkylketene dimers and related ketones in papers containing 0.025-1.0% of this sizing agent (B13). The technique was also used to determine styrene copolymer sizing agents in paper. Amounts of sizing agents were determined with a precision of about 1.4%relative standard deviation based on the styrene monomer yield. These data suggested that about 80% of the suing agents added in a pulp slurry were retained by the paper (BI4). Poly(methy1 methacrylate) end groups were determined by Py-GC using a chromatograph equipped for simultaneous detection with flame ionization, sulfur-selective flame photometric, and/ or nitrogen/phosphorus detectors. The technique was particularly useful to detect end groups associated with the AIBN initiator or chain-transfer reagents such as thioglycolic acid and mercaptopropionic acid (B15). Nanometer thick layers of poly(methy1 methacrylate) on the surface of poly(ethy1ene terephthalate) film were determined by pyrolysis-GC. A linear relationship was obtained between the yields of characteristic pyrolysis products and the thickness of the poly(methy1 methacrylate) layer without any pretreatment of the samples (B16). Polyimides, cross-linked resins formed from an aromatic diamine, an aromatic tetracarboxylic acid diester, and a monoester of 5-norbornene-2,3-dicarboxylicacid, were investigated by PyGC. Effects of the extent of cure, formulated molecular weight, and cumulative aging were studied in relation to the pyrolysis yield of cyclopentadiene (B17).The thermal decomposition of arylalicyclic polyimides was studied by Py-GC/MS and thermogravimetry. The pyrolysis yield of aliphatic and aromatic products was affected by the structure of the aliphatic segments in these polymers. The primary decomposition of the alicyclic moieties was an important step in the degradation mechanism (BI8). Block, random, and block-random ethylene-vinylcyclohexane copolymers prepared in different ways were examined by Py-GC/ MS. Random copolymers were prepared using a Ziegler-Natta catalyst at constant ethylene pressure, and block vinylcyclohexane units were observed in copolymers prepared with nonstationary conditions. Yields of appropriate pyrolysis products were related to the block units in these copolymers (B19). The technique was also applied to study the composition and sequence distribution of monomer units in butadiene-isoprene copolymers containing 5-33 mol%butadiene. Concentrations of diads and triads in the
copolymers were measured from the pyrolysis yields of homo and hybrid dimers and trimers (B20). Linear and cyclic perfluoroalkanes were pyrolyzed at 900 "C. Perfluoropentane and perfluorohexane yielded the highest amounts of perfluoroisobutylene (B21). Pyrolysis-GC was also used to characterize polymeric additives in oils. The technique was used to evaluate multicomponent alkyl methacrylate copolymers that comprise a common group of viscosity improvement polymers (B22). Poly (di-n-alkylsilylene) copolymers of the type (R2Si) ,,(R'ZSi), were prepared where R and R' included methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, but R and R' were not the same alkyl moieties. Thermal transitions, measured by differential scanning calorimetry (DSC), and nuclear magnetic resonance (NMR) spectra were obtained for the copolymers and homopolymers, and copolymer compositions (nlm ratio) were determined by Py-GC/MS and solution NMR (B23). In a related publication, one of these workers documented pyrolysis conditions for degradation of poly(dialkylsily1enes). Degradation, beginning at 200 "C, proceeded through the formation of cyclic oligomers. At 300 "C, copolymers containing dimethylsilylene units produced tetra- and pentacyclic compounds, while copolymers containing ethyl and higher alkyl units produced only tetracyclic compounds (B24). Curie point high-resolution gas chromatography with different spectroscopic detection systems (mass spectrometry, infrared, atomic emission) was used to characterize cured epoxy resins. The AED was particularly useful in detecting element-spec& pyrolysis products related to minor components such as coupling agents (B25). Other workers observed phenols and the glycidyl ethers of Bisphenol A in the pyrograms of epoxy resins cured with prepolymers of different molecular weights. Peak intensities increased with increasing molecular weight of the prepolymer (B26). Pyrolysis-GC/MS was also used to identdy components of carbon-fiber composite containing epoxy resins such as N,N,N'tetraglycidyl-4,4'-diaminodiphenylmethane,the diglycidyl ether of Bisphenol A, and the accelerator 3-(3,4dichlorophenyl)-l,1-dimethylurea. Components identified in another composite cured at 175 "C included N,N,N'-tetraglycidyl-4,4'-diaminodiphenylmethane, a polysulfone, and another component that yielded aminophenols (B27). Furfuraldehyde resins and poly(pheny1-as-triazenes) were among the miscellaneous polymers examined using pyrolysis techniques. A total of 38 products were identified from the pyrolysis of furfural homopolymer and an acetone-furfural copolymer using Py-GC/MS and infrared (IR) spectroscopy (B28). More than 12 products from the pyrolysis of poly(pheny1-astriazines) at temperatures between 650 and 900 "C were identified by mass spectrometry. Results of these Py-GC/MS experiments were combined with thermogravimetric data to provide information on the mechanisms for degradation of this polymer (B29). Curie point pyrolysisGC/MS was used to differentiate between hydrocarbon polymers such as low-density polyethylene and ethylene propylene-norbornene modified copolymers. This technique and temperature-programmed mass spectrometry were used to identify these polymers and others in complex mixtures (2330). Curie point pyrolysis was also one of several techniques used to determine the composition of an uncured polyester resin
containing an acrylate copolymer, a cross-linking accelerator, surfactants, and other additives (B31). Plasma-prepared polypyrrole was characterized by pyrolysisGC/MS and infrared spectrometry. Major thermal decomposition products were nitriles with fewer than four carbon atoms and monosubstituted alkylpyrroles such as 2-methylpyrrole or Bethylpyrrole. Evolution of the linear nitriles suggested that the polymer contained nitrogen atoms in the main chain (B32). Copolymers of 1-vinyl-2-pyrrolidoneand 1-vinyl-3methylimidaze lium chloride, used in cosmetic products, were analyzed by pyrolysis-GC/MS (B33). Cationic and anionic ionexchange resins were also characterized using a foil pulse pyrolyzer. Cationic resins released mainly SO2 and benzene at a pyrolysis temperature of 500 "C, whereas ethylbenzene, styrene, HZS, and toluene were additional products detected at higher pyrolysis temperatures. The anionic resins generated trimethylamine and methyl chloride at 400 "C and styrene, p-methylstyrene, and p-ethylstyrene at higher pyrolysis temperatures up to 900 "C (B34). LIQUID CHROMATOGRAPHY Several reviews and tutorial-type articles were written on the characterization of polymers by size exclusion chromatography (SEC) and high-performance liquid chromatography (HPLC). Included among these were reviews of liquid chromatography (LC) (applied to polymer characterization) (CI),SEC (CZ), alternatives to SEC (C3), problems associated with aqueous SEC (C4), and basic principles of analytical SEC (C5). New directions in SEC were also discussed in a summary format (C6). A tutorial on SEC characterization of pectins and water-soluble cellulosic materials was written (C7). HPLC for characterization of copolymers was reviewed (C8, C9). The proceedings of the 1991 ACS Symposium on Chromatography of Polymers were published in an ACS Symposium Series book (CIO),comprising four sections: Field-Flow Fractionation; Size-Exclusion Chromatography: Fundamental Considerations; Size-Exclusion Chromatography: Viscometry Detection; and Size-Exclusion Chromatography: High-Temperature, Ionic, and Natural Polymer Applications. Volume I1 of the Handbook of Chromatography relating to Polymers was issued (C11). The solution properties of several polyelectrolytes including sodium poly(styrene sulfonate) (NaPSS), poly(acrylic acid) (PAA), and poly(r;glutamic acid) were studied under a variety of aqueous SEC conditions (C12-C15). SEC-viscometrywas used to assess the applicability of the universal calibration principle for characterization of PAA by aqueous SEC (C16). Cationic and anionic polyelectrolytes including protonated poly(2-vinylpyridine),poly(2-vinylpyridinium benzyl bromide), and NaPSS were characterized by aqueous SEC on a single type of packing material with differing mobile phases for the anionic and cationic samples (C17). Aqueous SEC coupled to low-angle laser light scattering (LALLS) and viscometry was applied to the anionic and cationic polyelectrolytes NaPSS and copolymers of acrylamide and N,N,N-trimethylaminoethyl chloride acrylate (C18). Aqueous SEC-LALLS was used to determine molecular weight distributions of epichlorohydrin dimethylamine copolymers (C19, C20). Molecular weight distributions of poly(4vinylpyridine) were determined by SEC-LALLSin a mobile phase comprising 50% methanol and 50% aqueous 0.1 M LiN03 (C21). Aqueous SEC and dynamic light scattering experiments were used to study the ion exclusion Analyfical Chemistry, Vol. 67, No. 12, June 15, 1995
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behavior of dextrans in water (C.2). Several polysaccharides were investigated by aqueous SEC-LALLS (C23). Several papers regarding aqueous SEC analyses of poly(ethy1ene glycols) (PEG) were published including studies of pure oligo (ethylene glycols) as standards for SEC (C24, identilication of PEG molecular weights in pharmaceutical preparations (C25), investigations of the binding of sodium dodecyl sulfate to PEG (C26), the use of PEG as a probe of poly(acrylonitri1e) membrane pore sizes (C27), and correlations of hydrodynamic characteristics of PEG and poly(vinylpyrrolidone) with SEC retention volume (C28). Pyrenelabeled polyacrylamides were studied by aqueous SEC (C29). SEC-viscometry was used to determine the Mark-Houwink coefficients for fully hydrolyzed poly(viny1 alcohol) in aqueous NaN03 at 35 "C (C30). Several techniques including aqueous SEC were used to characterize the molecular structure and degradation behavior of poly(amido amines) (C31). SEC-LAUS viscometry and SEC coupled to differential refractive index @RI) and conductivity detectors were used to characterize aqueous solutions of carboxymethylcelluloses (C32). SEC was used to study fastcuring phenol-formaldehyde resins (C33) and aging of phenol-formaldehyde resins (C34). Oligo(thiophene-ethylene) derivatives were synthesized using an iterative approach and characterized by SEC (C35), and electrochemically synthesized poly(3alkylthiophene)s were characterized by SEC (C36). An algorithm for optimization of the SEC calibration curve for unknowns was developed and applied to the molecular weight determination of poly(viny1 chloride) (C37). Polyamides were characterized by SEC in hexafluoro-2-propanol containing 0.1%sodium trifluoroacetate, and the determined poly(methyl methacrylate) (PMMA) apparent molecular weights were correlated with absolute number-average molecular weights measured via end group analyses (C38). A variety of fluorine-containing polymers were characterized by SEC including fluoropoly(oxyalky1enes) in 1,1,2-trifluorotrichloroethane (C39), copolymers comprised of vinylidene fluoride (VF) /hexatluoropropylene (HFP) , VF/HFP/tetratluoroethylene (FE) ,VF/HFP/TFE/bromoperfuoropropylene (BPFP) , and VF/ TFE/BPFP/perfluorovinyl methyl ether in tetrahydrofuran (C40) and perfluoro ether compounds on fluorinated gels that were compatible with fluorinated solvents (C41). The SEC elution behaviors of polyamide-imide and polyamic acid in N,N-dimethylformamide were studied as a function of mobile-phase electrolyte content (C42). Several techniques including SEC were used to investigate poly(dimethylsi1oxane) -urea-urethane copolymers containing 1,4benzenedimethanol as a chain extender (C43). Liquid crystalline polymers containing siloxane side chains were studied by a variety of techniques including SEC in methylene chloride (C44). The thermal stabilities of poly(styrene-blockmethyl methacrylate) and poly (styrene-block-ethylene-cpl-buteneblock-methyl methacrylate) were studied by SEC (C45). The conversion of a substituted poly(cyc1ohexadiene) precursor polymer to poly@-phenylene) was investigated by SEC (C469, and the technique was used to characterize star-branched polystyrene (PS) (C47), epoxy-terminated PS (C48), and the kinetics of ultrasonic degradation of PS in toluene solutions (C49). SEC and NMR were used to characterize hydroxy-terminated polybutadienes, and the results were correlated with binder mechanical properties (C50). Ozonolysis followed by SEC was used to analyze the sequence distribution of 1,2 units in a polybutadiene sample containing 57.2%1,2 units (C51). Selective 102R
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ozonolysis followed by SEC was also used to determine the crystalline stem length and stem length distribution in truns-1,4 polyisoprene (C52). Techniques were developed and applied to the characterization of SRM 1480, a low molecular weight polyurethane standard for SEC calibration (C53). The effects of stoichiometry and monomer type on polyurethane prepolymer reaction kinetics were studied by SEC characterization of quenched samples (C54). Molecular weights of polyaniliies, in the emarldine and leucoemarldine base forms, were studied by SEC (C55C57). High-temperature SEC was used to determine apparent molecular weight distributions of anionically polymerized ethylene (C58), poly(pheny1ene sulfide) in 1-cyclohexyl-2-pyrrolidinoneat 210 "C (C59), and anionically polymerized 4vinylpyridine and block copolymers of 4vinylpyridme and methacrylates in N-methyl-2-pyrrolidinone at 90 "C (C60). High-temperature SEC chromatograms of high-density polyethylene were deconvoluted into a series of Flory distributions (C61). Temperature-rising elution fractionation (TREF)-SEC was applied to impact-resistant polypropylenes containing poly(ethy1eneco-propylene) (C62). A vortex mixer was used to expedite the sample preparation for high-temperature SEC characterization of polyolefins (C63). Several papers concerning SEC of PEG and PEG copolymers were published including studies of the molecular mass dependence of preferential solvation of PEGS in chloroform/ethanol mixtures of varying composition (C64), the elution behavior of PEG from a hydrophilic gel packing in a variety of mobile phases (C65), and apparent molecular weight distributions of PEG/poly(propylene glycol) copolymers (C66). A procedure for SEC calibration was developed for, and applied to, determination of molecular weight distributions of poly(imidesiloxane) copolymers (C67). Fast-atom bombardment mass spectroscopy and SEC were used to characterize moderately sized dendritic macromolecules based on the 1,3-diaminopropan-2-01 pivotal molecule (C68). High-temperature SEC coupled to IT-IR was studied extensively and applied to ethylene/propylene copolymers (C69), and homopolymers and blends of PS, polyethylene, and polypropylene (C70). TREF fractions of ethyleneh-butene copolymers were characterized by SEC, off-line IT-IR, and other techniques (C71). SEGIT-IR was used to determine the compositions of PS/PMMA blends as a function of SEC retention volume (C72). SEC employing dual-concentration detectors was used to determine the bulk composition and composition versus retention volume for block copolymers of polyacenaphthylene-polyisobutylene (C73), and PEG/poly(propylene glycol) blends (C74). SEC coupled to UV/visible spectroscopy was used to study color formation in styrene-acrylonitrile copolymers (C75) and the incorporation of methyl vinyl ketone in copolymers with styrene (C769. A FT-Raman detector for SEC was developed and applied to the microstructural characterization of polybutadiene, but the overall sensitivity of the detector was too poor to provide quantitative information on polybutadienes eluting from an SEC column (C77). The effects of operating conditions, including flow rate and column packing particle size, for determining the molecular weight distributions of high molecular weight polyethylenes (C78) and the solution-phase degradation of poly(phenylacety1ene) in THF solutions were studied by SEC-LALLS (C79). A new mobile phase comprised of methylene chloride and dichloroacetic acid was used for SEC-LALLS studies of poly(ethy1ene terephthalate) (C80) and
various nylon molecular weight distributions (C81). Molecular weight distributions of two- and three-component polyetherpolyurethanes were determined by SEC-viscometry and SECU L S (C82).This latter technique was also used to study the “prehump 11” in the SEC chromatogram of cellulose acetate in acetone (C83). Independent calibration of molecular weight sensitive detectors in SEC-multidetectorexperiments was applied to the characterization of PS and PMMA (C84).A new approach for determining the interdetector lag time in SEC-multidetector experiments was discussed and applied to SEC-multiangle laser light scattering (MALLS) characterization of PS (0. SECLALLSviscometry was applied to irradiated PS, poly(a-methylstyrene), and PMMA (C86).PS samples of varying polydispersity and topology were studied by SEC-MALLSviscometry (C87).The weight-average molecular weights and radii of gyration of narrowfraction PS molecular weight standards were determined by SECMALLSviscometry in 1,2,4trichlorobenzeneat 140 T (C88).The solution properties of an all-aromaticliquid crystalline copolymer synthesized from terephthalic acid, phenylhydroquinone, and (1phenylethyl)hydroquinone (2:l:l) were studied by SEC-LALLS viscometry (C89). Molecular weight averages and limiting viscosity numbers for a series of poly(phenylacetylenes), synthesized by polymerization with a variety of tungsten and molybdenum catalysts, were determined via SEGLALLSviscometry(C90). Trifunctional, randomly branched poly(cyanurates) were studied by SEC-ULSviscometry (C91). Static MALLS was used to determine the weight-average molecular weight, the second vinal coefficient, and the radius of gyration of natural rubber in toluene (C92). An analytical approach for estimating the interdetector delay volume was discussed and applied to the SEC-MALLScharacterization of poly(ethylene oxide) (C93).Epoxy, phenoxy, novalac, polyester, and alkyd resins were studied by SEC-MALLS (C94),and peak broadening was determined and corrected for in the SEC-LALLS characterizationof controlled rheology polypropylenes (C95).SEG MALLS was also used to determine the molar masses and radii of gyration of dialkyl and aryl-alkyl-substituted polysilanes as they eluted from an SEC column (C96)and the molecular weight averages and molecular weight distributions for some polyurethane elastomer samples (C97).Molecular weight data for PS and polybutadiene (standard reference materials) were obtained via SEC and SEC-MALLS and were compared to literature data (‘298).Microgel formation in copolymers of 4tert-butylstyrenel 1,4divinylbenzene was studied by SEC-MALLS (C99). A low-pressure SEC system was coupled to a modified Ubbelohde capillary viscometer and applied to determining molecular weights and long-chain branching in polychloroprene (C100). The use of SEC-viscometryfor determining the numberaverage molecular weight of polymers (NBS 706 PS) was critically evaluated (C101). Quantitative high-temperature SEC employing DRI and viscosity detectors for characterization of polyolefins was discussed (‘2102). Calibration, determination of Mark-Houwink coefficients (C103), resolution correction, and determination of the interdetector volume (C104) in SEC-viscometry were discussed for studies of PS and polyethylene. An alternative approach for establishing universal calibration curves was applied to SEC-viscometry characterization of broad molecular weight distribution polyethylene and PS samples (C105). SEC-viscomebywas also used for determining number-average molecular weights and for estimating polydispersities for several
types of polymers including PS, PMMA, poly(dimethylsiloxane), and blends of PMMA and poly(dimethylsi1oxane) (C106). SECviscometry was used to determine molecular weight distributions, Mark-Houwink coefficients, and dissolution of poly(viny1 chloride) in 1,2,4trichlorobenzene at 110 “C (C107). The molecular weights of poly(amide acid) samples were determined by SECviscometry (C108). The Mark-Houwink-Sakurada and Dondos-Benoit viscometric constants were determined for low molecular weight polyisobutenes and polystyrenes by SECviscometry (C109).Off-line osmometry, viscometry, light scattering, and SEC were used to determine absolute molecular weight averages and the Mark-Houwink coefficients for poly(2,&dimethylphenylene oxide) in toluene at 30 “C (C110), absolute molecular weight averages and hydrodynamic properties of poly[&I41 (4methoxyphenoxy)carbonyllphenoxylhexyl methacrylate] in a variety of solvents (C111), and molecular weight distributions and Mark-Houwink parameters for a variety of poly(fluorostyrene-co-chlorostyrene) copolymers (C112). Separations near the “critical range” of LC were reported for a number of block copolymer systems and polymer blends including poly(ethy1ene oxide)-poly(propy1ene oxide) block copolymers (C113),poly(styrene-block-methyl methacrylate) s ((214, poly(decy1 methacrylate-block-methyl methacrylate)^ (C115, C116), and poly(methy1 methacrylate) -poly(vinyl chloride), PMMA/PS, and PMMA-poly(styrene-co-acrylonitrile) blends (C117). Sudden transition gradient HPLC was used to determine composition distributions of a variety of copolymers including styreneethyl methacrylate, styrene-methyl methacrylate, and styrenemethoxymethyl methacrylate (C118-C120) and styreneacrylonitrile (C121). The elution behavior of styrene-acrylonitrile copolymers was studied by HPLC in mixtures of chloroform and n-hexane as mobile phases (C122, C123). Styrene-n-butyl methacrylate and styrene-tert-butyl methacrylate copolymers were separated according to chemical composition by gradient normalphase and reversed-phase HPLC (C124). Normal-phase gradient HPLC was used to separate methyl methacrylate-methacrylic acid copolymers according to chemical composition (C125). Ozonolysis, followed by HPLC was used to study the sequence distribution of styrene units in styrene-butadiene copolymers (C126). The retention behavior of a variety of polymers on silica was studied under a variety of eluent conditions (C127). Functionalized dendritic macromolecules were separated by reversed-phase HPLC (C128). Several reports were published concerning investigations of micelle formation among block copolymers including characterization of poly(ethy1ene oxide-block-propylene oxide-block-ethylene oxide) by SEC (C129,C130),characterization of poly(styreneblock-isoprene) by SEC in a variety of solvents (C131),characterization of poly (styrene-block-methyl methacrylate) by SECLALLS (C132),and characterization of poly(styrene-blockmethacrylic acid) and poly(methacrylic acid-block-styrene-blockmethacrylic acid) by quasielastic light scattering and sedimentation velocity experiments (C133). Low molecular weight oligo (ethylene glycols) were separated by HPLC (C134-CI36). Reversed-phase HPLC was used for characterization of PEG, poly(propy1ene glycol), and polyfiutylene glycol) oligomer distributions (C137).A polydisperse mixture of octylphenoxy poly(ethoxy)ethanol oligomers was characterized by SEC coupled to electrospray ionization MS (C138). HPLCET-IR was used to characterize an isodecyl end-capped, propylAnalytical Chetnistty, Vol. 67, No. 72,June 15, 7995
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enediol adipate polyester sample (C139). Tributylphenol ethylene oxide oligomeric surfactants were separated by HPLC on alumina supports (C140). Charged and uncharged, oligomer-like model compounds were separated by HPLC using mixed-mode (reversedphase/anion-exchange) stationary phases (C141). Hydrolytic fusion followed by reversed-phase HPLC was used for determination of the composition of some liquid crystalline aromatic polyesters (C142). Alkali hydrolysis followed by HPLC was used to characterize biodegradable polyesters containing lactic acid and glycolic acid (C143). Supercritical fluid chromatography (SFC) was used to separate polyethoxylated nonylphenol surfactants (C144). Micro-SEC coupled to GC and LC was used for sample cleanup and determination of additives in polycarbonate and acrylonitrile-butadiene-styrene samples (C145). MASS SPECTROMETRY
This portion of the review will cover topics pertaining to the application of mass spectrometric techniques to the characterization of polymers and rubbers. Various reviews were written in this area, with most of them relating to the application of mass spectrometry to the surface analysis of polymers. The surface analysis reviews were broad overviews of the use of various complementary surface analysis techniques and so they were not limited to the discussion of mass spectrometry. The capabilities of static secondary ion mass spectrometry (SIMS) for the surface analysis of polymers was reviewed (01). The application of SIMS to the study of interfacial adhesion for high-performance polymeric adhesives and composites was reviewed (DZ), and the most important developments over the past 30 years in static SIMS for surface analysis were reviewed (03). Instrumentation, ion-formation processes, quantitative analysis, and use of derivatizing reagents for time-of-fight (TOF)-SIMS were reviewed (04). A review of the study of polymer surfaces at Sheffield University over a six-year period covered the application of TOF-SIMS and SIMS to a variety of surface problems (05). Reviews also appeared on the use of high-resolution tandem FTMS for polymers at greater than 10 kDa (06) and the accurate measurement of polymer molecular weight distributions using matrix-assisted laser desorption ionization (WILDI) MS (07).A review of the use of FTMS or TOF-MS as a detector for laserdesorbed neutral species reported on the formation of ions by resonant or nonresonant laser ionization. Ionization selectivity was achieved by using different wavelengths for the postionization step (08). Static SIMS and TOF-SIMS were used extensively in surface analysis applications and in combination with laser ionization techniques for general polymer analysis applications. Polystyrene functionalized with perfluoroalkylchlorosilane,a butadiene polymer, and polystyrene coated with a silver overlayer were analyzed using static TOF-SIMS (09). The surface compositions of random copolymers of poly(styrene-&-styrene) were studied using static SIMS. The extent of deuterium incorporation in the various fragment ions was beneficial for understanding the mechanism of fragmentation during the SIMS process (010). In a similar study, a mixture of perdeuteriopolystyrene and perhydropolystyrene, analyzed by TOF-SIMS, indicated that no observable H/D exchange occurred between small polystyrene fragments (8003000 Da) or oligomers. This suggested that hydrogen-transfer processes related to polymer fragmentation in SIMS occurred via an intramolecular mechanism (011). 104R
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An on-line combination of TOF-SIMS and monochromatized photoelectron spectroscopy was used to investigate microwave (2.45 GHz) nitrogen plasma-moditied polystyrene surfaces (012). A high-resolution TOF-SIMS instrument was used to systematically investigate the reproducibility and accuracy of mass measurement from 0 to 600 Da for a thick film of poly(ethy1ene terephthalate) sample. An accuracy of better than 20 ppm was achieved over this mass range using routine operating conditions. The effects of a polymer additive, such as glyceryl monostearate, was also studied (013). TOF-SIMS was used to investigate a series of poly(alky1 acrylates) (PAA) and poly(alky1 methacrylates) (PAM). The reproducible spectra were composed of clusters of silver cationized neutral fragments of the main polymer chain. The effect of different alkyl groups on the fragmentation patterns of PAAs was discussed, and PAA and PAM spectra were compared (014,015). Perfluorinated polyethers and their van der Waals dimers were analyzed using resonance-enhanced two-photon ionization TOF spectroscopy. The polymers were laser vaporized and entrained in a pulse jet expansion. Two-photon ionization of the cold polymer via the phenoxy chromophore was combined with TOFMS for polymer molecular weight distributions up to 7000 Da. Under certain conditions, parent masses were observed for van der Waal dimers (016). TOF-SIMS was used to characterize PEG and PPG samples over the 400-100000 Da molecular mass range (017) and polybutadienes with molecular masses between 400 and 170 000 Da (018). The number-average and weight-average molecular weights determined were comparable to those obtained using conventional methods. Fragmentation mechanisms were discussed, and fragmentation cluster intensities were studied as a function of sample molecular weight and cluster size. Laser-desorption TOF and field-desorption MS (FDMS) were used to analyze plasma-polymerized C ~films O prepared under Ar plasma (019). Static TOF-SIMS was used to determine tracelevel polymer additives in linear low-density polyethylene. Information on additive surface migration and surface oxidation was also obtained in this study (020). Matrix-assisted laser desorption ionization TOF-SIMS was used to characterize nonpolar polymers containing ferrocene, ferrocenylnaphthalene, and ruthenocenylnaphthalene groups in their repeating units. Radical molecular ion formation was shown for polymer samples in the range of 1-13 kDa. A method of verifymg the formation of radical molecular ions was described (021),and laser ionization mass spectrometry was used to study the fragmentation of FeC13-doped poly@henylacetylene) (022). Absolute mass values in MALDI TOF-MS were determined using a new self-calibration procedure whereby a best-fit minimization was performed. Application of the procedure was demonstrated using poly(capro1actone) and poly(Bispheno1A carbonate)with interpretation of single peaks up to 20 kDa (023). The application of MALDI to PVC, PVA, polycarbonates, and other polymers was made possible by the use of simple solvents such as acetone, THF, and methanol during sample preparation (024). MALDI was used to characterize commercial light stabilizers of less than 5000 average molecular weight. The MALDI results compared favorably with field desorption spectra with regard to providing both molecular weight information and structural information. Although field desorption generally can provide higher ionization efficiencies for higher molecular weight
species, the MALDI technique was better at providing consistent spectra from the same sample, which made it more useful for batch comparisons (025). Molecular weight distributions obtained from MALDI-MS compared favorably with gel permeation chromatography (GPC) results obtained from the analysis of oligomers derived from ((I?)3-hydroxybutanoates) with less than or equal to 96 monomer units. The oligomeric distribution from partial depolymerization of the polymer was also studied (0269. Several examples of polymer characterization using Fourier transform mass spectrometry (FTMS) (also referred to as FT ion cyclotron resonance (FTICR)) were discussed. Silver ion chemical ionization of nonpolar hydrocarbon polymers, such as polystyrene, polyisoprene, polybutadiene, and polyethylene, was accomplished by the addition of silver nitrate to the polymer solutions prior to analysis by laser desorption FTMS. Silverattached oligomer ion distributions were observed, and these polymers did not yield useful mass spectra under conventional laser desorption conditions (027).Copper, silver, and gold gasphase ions attached efficiently to polybutadiene in laser desorption time-of-flight experiments. In this case, the polymer was s u p ported on a probe tip of the appropriate metal (028). The trapping, detection, and mass measurement were described using ETICRfor individual ions from poly(ethy1ene glycol) and sodium poly(styrenesulfonate). A scheme was developed for charge site determination based on observation of stepwise mass shifts resulting from charge-exchange reactions or adduct formation with substances of known mass. Mass determination of individual ions was accomplished using a novel technique called time-resolved ion correlation (TRIC) (029). Desorption chemical ionization (CI) MS of oligomers remaining in the reaction solvent from polymer synthesis proved useful in providing structural information for ethylene-C0 and propylene-CO copolymers and ethylene-propylene-CO terpolymer. Not all polymeric structural features could be deduced from the oligomeric spectra, but information was attained on terminal groups, monomer linkages, and molecular weight distributions (030). A multiplicative correlation algorithm (MCA) was developed for improved processing of electrospray ionization mass spectra. Accurate mass determinations using less sample were possible with this algorithm as compared to previous algorithms. Factors were discussed for affecting optimal MCA performance (031). Evolved gas analysis techniques (thermal desorption, TG/MS, etc.) were applied extensively for polymer characterization and degradation analyses. Degradation of paint films on thermoplastics was investigated using thermal desorption-GUMS (032). This technique was also used as a high-sensitivity (10-100 ppb) technique to characterize the outgasing of polycarbonate materials that were used as microenvironments (i.e., miniature clean rooms) for wafer processing and storage (033).Argon and DzO were purposely entrained in Bisphenol A polycarbonate so that their emission during deformation of the polycarbonate could be monitored using quadrupole mass spectrometry. Emission increases were noticed during transient loading events, which resulted in strainenhanced diffusion of the occluded volatiles (034). Direct pyrolysis and evolved gas analysis techniques were used to characterize the degradation products of poly(ethy1ene oxide). Direct C-0 and C-C bond scission of the polymer backbone
occurred using pyrolytic heating, whereas evolution of small molecules such as ethyl ether and acetaldehyde resulted from the controlled thermal degradation of the polymer (035).Lineartemperatureprogrammed (i.e., 10 Wmin) pyrolysis-MS (LW-PyMS) and FT-IR (LTP-Py-FT-IR) techniques were used to investigate the thermal degradation of aromatic polyethers and polyetherketones (036). An experimental apparatus for TG/GC/MS and TG/GC/IR was used to analyze poly(a-methylstyrene) and a styreneisoprene block copolymer (037).A simple degradation model was proposed for the thermal degradation of radiation-grafted and sulfonated telraftuoroethylene-hexatluoropropane copolymer @El')graft-polystyrene membrane, which was investigated over the temperature range of 50-650 "C using TG in combination with FT-IR and MS (038). Evolved gas analysis was used as a complementary technique to thermal, spectroscopic, and surface analysis techniques for materials characterization. The purity of acrylic polymer coatings on optical disks was characterized using TG/MS, STM, DMA, IR, and TG (039).Cross-linking reactions of a new monomer for the synthesis of thermally cross-linkable rigid-rod aramids was CP-MAS investigated using TG/MS along with TG, FllIR, NMR, and ESR (040). TWMS was also used to study the thermal degradation of postchlorinated poly(viny1 chloride) (043,polystyrene, poly@methylstyrene), poly (a-methylstyrene) (042),poly(carbosi1anes) (043),flame retardants, and fire-protected polymers (044). Photodegradation products from UV exposure of polystyrene strips in an ultrahigh vacuum chamber were identified using MS. The results provided the first conclusive evidence that phenyl radicals were formed during the photolysis of polystyrene film (045). Several applications of mass spectrometry to the analysis of rubber materials were discussed. Supercritical fluid chromatography combined with MS (E1 and CI) was used to determine cylic siloxanes in silicone rubber. Ammonia was the best CI reagent gas for the CI-MS analysis of higher molecular weight cyclic siloxanes. MALDI-MS was used as a complementary method for the characterization of the cyclic siloxanes in the higher molecular weight range (0469. G U M S was also applied to identify the extensive cracking products from the thermolysis of cis-polyisoprene rubber in supercritical toluene. Scrap rubber from an isoprene rubber aircraft tire yielded similar results (047). NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY Several books and reviews were written on the characterization of polymers by NMR (E1-E4) and by solid-state NMR (E5-E7), NMR of industrial polymers (E@, and NMR and the fractal properties of polymer solutions and gels (E9).The NMR imaging of polymers was reviewed (E10)as was NMR imaging of solid polymers ( E l l ) . Pulse field gradient NMR studies of chain molecules in polymer matrices were reviewed (El2)as was the use of 12%e NMR for studying polymer morphology (E13). The sequence distribution of copolymers was determined by high-resolution NMR for ethylene-a-methylstyrene copolymers (El4), a-methylstyrene-2-chloroethyl vinyl ether copolymers (El$, ethylene terephthalate-l,4cyclohexenedimethylene terephthalate copolymers (El@, lZoxydodecanoy1, o-iminoalkanoyl Analytical Chemistry, Vol. 67,No. 72,June 75,7995
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polyesteramides (E17), methyl methacrylate-ethyl acrylate copolymers (E18),styrene-ethyl acrylate copolymers (E19),styrenevinylidine cyanide or methylvinylidine cyanide copolymers (E20), vinyl acetate-methyl acrylate copolymers (E21), ethylene- 1decene copolymers (EZZ), fluorine-containing poly(ary1 ether sulfone) copolymers (E23),and substituted pphenylenevinyleneethylene oxide copolymers (E24). Sequence measurements were also made for styrene-acrylic acid copolymers (E25),styrenemethyl methacrylate copolymers (E26),acrylonitrile-butyl acrylate copolymers (E27), methyl methacrylate-methyl acrylate (E28), hydroxyethyl acrylate-methacrylic ester copolymers (E29), vinylidene cyanide-methacrylonitrile-cyanovinyl acetate copolymers (E30),ethylene-propylene copolymers (E31),methyl methacrylate copolymers with a-trifluoromethacrylic acid (E32),and copolyperoxides of styrene and methyl methacrylate (E33). Models were discussed for copolymer polydispersity ( E 3 4 and the effect of different catalytic sites in polyolefin polymerization (E35). Polymer stereochemistry was determined by high-resolution NMR for the following polymers; poly(n-butyl methacrylate) (E36), ethylene-propylene copolymers (E37),methyl(3,3,3-trifluoropropyl) siloxane (E38), citraconic anhydride-styrene copolymers (E39), poly(1-naphthylmethyl acrylate) and poly(2-(l-naphthyl)ethyl acrylate) (E40),polystyrenes (E41),poly(methy1vinyl ether) (E42), polypropene (E43, E44), propene-carbon monoxide copolymers (E45), ethylene-vinyl acetate copolymers (E46), citraconic anhydride-fi-chlorostyrene copolymers (E47), poly(methyl methacrylate) (E48),and poly (diallyldimethylammonium chloride) (E49). A probability model was presented for treatment of regio- and stereoirregular polymers (E50). Copolymers of glycidyl methacrylate and n-vinylpyn-olidone (E51), poly(2-vinylselenophene) (E52), poly(2-vinyl-5methylthiophene) (E53),poly(3bromostyrene) (E54),poly(2-thienylvinyl ketone) (E55),copolyesters of ethylene glycol, terephthalic acid, and hydroxybenzoic acid (E56), poly (n-methyl-2-vinylpyrrole) (E57),copolymers of chloroprene with maleic anhydride (ESS), methacrylic acid-ethyl acrylate copolymers (E59),poly(n-vinyl2-oxazolidone) (E60),poly(ary1 ether ketone) and poly(ary1 ether sulfone) oligomers (E61),isomerized polybutadienes (E62),and oligomers of 1,4butanediol and toluene diisocyanate (E63) were characterized by high-resolution NMR This technique was also used to study model epoxy networks based on the diglycidyl ether of Bisphenol A (E64), resorcinol-formaldehyde resins (E65), urea-fonnaldehyde resins (E66),poly(1-naphthylalkyl methacrylates) (E67),polyesters from diethylene glycol, cis- and trans-4cyclohexene-l,2-dicarboxylicacid (E68), polyesters from 3-hydroxybutyrate and 3-hydroxyvalerate (E69), poly(n-benzoyl-8octanelactam) (E70), poly(2-vinylpyridme) (E71),sidechain liquid crystalline polymers based on poly(dipropargy1amine) main chain (E72),polyaniline (E73),poly(2-trimethylsiloxy)butadiene (E74), poly(2,2,2-trifluoroethyl methacrylate) (ET@,and copolymers of diphenyl ether with 28 of its chlorinated derivatives (E76). Graft copolymers of methyl methacrylate with ethyl acrylate on amylose (E77) and water-based epoxy-acrylic graft copolymers (E78) were also characterized by NMR The distribution of functionality was determined for polyether polyols by 13CNMR spectroscopy (E79). The polymerization of ethylene with an awllithium catalyst was characterized (E80) as was the anionic (E81)and organotinalkyl phosphate polymerization of propylene oxide (E82). The 106R
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side reactions in anionic polymerization of acrylonitrile were studied (E83). NMR was used to characterize the end groups of poly(propy1ene oxide) (E84),poly(pheny1 glycidyl ether) (E85, E86), poly(2,&dimethyl-l,4phenylene oxide) (E87), and endfunctionalized polyisobutylenes (E88). A method for the quantitative functionalization of poly(ethy1ene glycol) end groups was discussed (E89). Transestedication reactions were studied by I3C NMR for a polyarylate, poly(l,4butylene terephthalate) system (E90) and a polycarbonate, poly(ethy1ene terephthalate) system (E91). The 14N quadrupole splitting of I4NH4' ion was used to probe the structure and orientation of ion-exchange membranes (E92). The degradation of poly(amido amines) was characterized by high-resolution NMR (E93). Ultrasonic degradation of high molecular weight polymers was shown to reduce their viscosity and, thereby, improve the quality of their NMR spectra (E94). The microstructure and conformations of piezoelectric poly(vinylidene cyanide-co-vinyl formate) were characterized (E95). High-resolution two-dimensional NMR techniques were used to determine molecular interactions of polyureas in DMF solution (E961 and the interactions that give rise to miscibility in poly(methyl acrylate) -poly(vinyl acetate) blends ( E 9 3 and in blends of polystyrene with poly(4vinylphenol) and sulfonated polystyrene with poly(N,N-dimethylacrylamide)(E98). The mode of styrene termination in free-radical polymerization was probed using 2-D INADEQUATE NMR (E99). Reactions between cyanate and epoxy resins were investigated using solid-state, 1-D, and 2-D NMR methods (E100). Two-dimensional NMR methods were used to characterize stereochemistry for tert-butyl acrylate oligomers (E101), polyepichlorohydrin (E102),PMMA (E103),poly(methacrylonitrile) (E104, E105), poly(acrylic acid) (E106), poly(viny1 chloride) (El07),polyacrylates (E108), y-irradiation canal-polymerized polyacrylonitrile (El09) and poly(propy1ene oxide) (E110). Macromolecular hydration was studied by 2-D heteronuclear 13C-IH separation spectroscopy (El1I). The solution conformations of aromatic copolyesters were studied by 2-D NOE experiments (E112). Molecular dynamics were investigated for vinyl chloridevinylidene chloride copolymers dissolved in tetrahydrofuran (E113) and poly(viny1 chloride) in dibutyl phthalate and tetrachloroethane (E114). Molecular dynamics were also characterized for stereoregular poly(methy1 methacrylate) in a homologous series of n-alkyl acetate solvents (E115),for linear poly(ethy1ene oxide) (E116-El18) and poly(tetramethy1ene oxide) in dilute solution (E119), for poly(1-naphthylmethyl acrylate) in dilute solution (E120-E121),for hydrated a,w-dicarboxylatopolybutadiene (E122),for polybutadiene in dilute solution (E123),and for aryl-aliphatic polyesters in solution (E124). 'H NMR was used to study the conformations of vinyl alcohol, vinyl acetate copolymers in DzO (E125), and model polyamide compounds (E226). The interactions between polyether-polyurethanes with other polyurethanes in solution were characterized by lH NMR (E127) as was hydrogen bonding in polyester-polyurethanes (E128).13C NMR relaxation studies were used to probe the hydrodynamic behavior of ionically terminated polytetrahydrofuran (E129). The reactivity ratios for copolymer polymerization were determined using NMR for free-radical-polymerizedallyl acetate with methyl methacrylate, with styrene, and with n-butyl acrylate (E130),for vinyl acetate-butyl methacrylate copolymers (E131), for acrylonitrile with vinyl acetate (E132),for styrene with methyl methacrylate in ternary oil-in-water microemulsions (E133),for
styrene with methyl methacrylate (E134,and for the copolymerization of 3-methoxy-4-[2-hydroxy-(3-methacryloloxy)propoxy]benzaldehyde with methyl methacrylate (E135).Curing reactions were characterized for cyanate resins (E136)and for epoxy resins with dicyandiamide (E137).A model for the copolymerization of ethylene with 1-octenewas developed (E138)and for citraconic anhydride with p-chlorostyrene (E139)and with styrene (23140). In situ NMR methods were used to investigate the polymerization of NJV,N’-tetramethyl-a, o-alkanediamines with dibromoalkanes (E1411 and the living cationic polymerization of isobutyl vinyl ether (E142).The structure of the propagating species was investigated for the cationic polymerization of n-benzoyl-8-octanelactam (E143),for isoprene initiated by a,o-dilithiopolyisoprene (E144,for the anionic polymerization of methacrylates in the presence of aluminum alkyls (E145),for the anionic polymerization of acrylic monomers (E146-E151),and for polyisobutylene (E152).NMR was used to study the reactions of Cpr TiMeC1-methylalumoxane systems, which are catalysts for olefin polymerization (E153), and the effect of methylalumoxane preparations on activity for ethylene polymerization (El54). The stereochemical kinetics of grouptransfer polymerization of methyl methacrylate were investigated (E155),as were the kinetics of the Diels-Alder reaction of furan-containing comblike polymers with dimethyl butynedioate (E156).The cross-linking of polyacrylamide by formaldehyde was investigated by 13CNMR (E157). The interaction between polymers and surfactants in dilute solution were determined for hydroxypropylmethyl cellulose, sodium dodecyl sulfate (E158),and anionic surfactants with hydrophobically modified poly(acry1amide) (E159).The adsorp tion of styrene-vinylpyridine diblock copolymers onto solid substrates was also investigated (E160), and NMR was used to study water absorbed in polybenzimidazole (E161). Polymer morphology was probed using I2Te NMR (E162El66). Optical pumping of xenon gas, used to greatly enhance its NMR polarization, was demonstrated in order to investigate polymer surfaces (E167,El68). Solid-state NMR was used to probe the miscibility of polymer blends. Proton TIQ measurements were used to determine miscibility in blends of polycarbonate with PMMA and PMMA copolymers (E169),poly(viny1 chloride) -PMMA-co-PMA blends (El 70),PMMA with poly(styrene-co-methacryonitrile) (El 71), poly(ecapro1actam)-polystyrene blends (El 72), polycarbonatepoly(ethy1ene terephthalate) blends (El731,poly(ccapro1actone) poly(viny1 chloride) blends (El 7 4 ,blends of oligo(ppheny1enevinylene) with polystyrene (El75),poly(3-octylthiophene)-poly(phenylene oxide) blends (El76,El 77),blends of Nylon 6 with sulfonated polystyrene ionomers (El78),and polystyrene-tetramethylbisphenol A blends (El79). Blends of poly(buty1ene terephthalate) with polyarylate (El80), poly(ethy1ene terephthalate) blended with poly (p-hydroxybenzoicacid-co-p-hydroxynaphthoic acid) (E181), poly(viny1 alcohol) -poly(n-vinyl-2-pyrrolidone) blends (E182),PMMA-poly (ethylene oxide) blends and poly(vinylpyrrolidone) -poly(acrylic acid) blends (E183), the effect of tacticity of PMMA on its miscibility of poly(styrene-cwinylphenol) (E184), poly(viny1chloride) -poly(ethylene oxide) blends (E185), blends of poly(acrylic acid) with poly(acry1amide) (E186),and blends of poly(pheny1ene oxide) and rubber-modiiied polystyrene (El87)were also studied by NMR. The intimacy of mixing between perdeuterated poly(vinylethy1ene) and polyisoprene was studied by intermolecular cross-polarization (E188).
Proton spin diffusion was used to characterize blends of polystyrene with poly(xy1ene ether) (E189), polyacrylonitrile or poly(4vinylpyridine)with cellulose (Elgo), polystyrene with poly(2,&dimethyl-l,4phenylene oxide) (El91),polystyrene with and polyPMMA using 13C CP-MAS NMR for detection (El92), (2,&-dimethyl-l,4phenyleneoxide) with polystyrene by rotordriven 13C spin diffusion (E193). The miscibility of blends of poly(styrenecc4vinylphosphonic acid diethyl ester) with poly(pvinylpheno1) was studied by DSC, IR, and 31Pand 13CNMR (E194).NMR line shape studies were used to characterize interpenetrating polymer networks of crosslinked PMMA and polyurethane elastomers (E193 and blends of poly(vinylpheno1) with main-chain polyesters (El96). The interdiffusion of PMMA and poly(vinylidene fluoride) was determined by cross-relaxation between the protons and the fluorines (E197).A 2-D HETCOR experiment was used to identify hydrogen-bonding interactions in blends of poly(vinylpheno1) and polyacrylates (E198)and the compatibilityof NjV-diphenyl-NYbis (3methylphenyl) -1,l’-biphenyL4,4‘-diamine and polycarbonate (E199).A 2-D ‘H NMR CRAMPS method was used to probe miscibility of poly(ppheny1ene vinylene) model compounds with polycarbonate (E200).The mixing of poly(ethylenenaphtha1ene dicarboxylate), poly(ethy1ene terephthalate) blends was investigated using CP-MAS with delayed decoupling techniques (E201). The relationship between solid-state NMR relaxation measure ments and mechanical properties was investigated for poly(urethane acrylate)s (E202,E203),for Duroplastic low-stress materials (E.204, for styrene, butadiene emulsion copolymer gels (E205),and for poly(ether ether ketone) (E206). The crosspolarization rates for a variety of polymers (E207)and for several polyurethane elastomers (E208,E209) were related to their dynamic storage moduli. Solid-state 13C NMR was used to determine the molecular dynamics present in blends of poly(vinylphenol) with poly(ethy1ene oxide) (E210), in poly(fumarates) (E211, E212),in polymer-dispersed liquid crystals (E213-E215), and in a mesomorphic mainchain polyester (E216).Motional heterogeneity was studied for apdicarboxylatopolybutadiene (E217),for poly(n-alkylacrylamide) (E218), and for the motion of side groups in gels of cross-linked comblike polymers (E219). Motion in flexible polyurethane foams and poly(4methyl-1pentene) was characterized by solid-state 13C NMR relaxation measurements (E220,E221). Heteronuclear dipolar cross-correlated cross-relaxation methods were used to study polymer sidechain motions (E222). The effect of processing temperature on the interaction between diisodecyl phthalate plasticizer and poly(viny1 chloride) (E223)and plasticization in solid polymer electrolytes (E224was investigated by NMR relaxation measurements. The origin of transitions in styrene-isoprene diblock copolymers was investigated by 13CNMR line width measurements (E.225).Solid-state 13C NMR was used to characterize the enhanced dynamics due to sorbed COz into polyisobutene (E226,E227) and polystyrene (E228).Oxygen adsorption in poly(2,Mimethylphenyleneoxide) was studied by solid-state lH NMR spectroscopy (E229).Solidstate 19FNMR was used to investigate the sorption of fluorinecontaining aromatic molecules in several polymers (E230).The crystalline phase of gel-spun ultrahigh molecular weight polyethylene (E231)and the lamellar thickness of ethene-propene copolymers (E232)were characterized by solid-state 13C NMR Analytical Chemisfy, Vol. 67, No. 12, June 15, 1995
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Solid-state 13C CP-MAS NMR was used to characterize the stability of a urea-formaldehyde resin toward hydrolytic treatment ( ~ 2 3 3 )a, urea-formaldehyde resin made from NJV-dimethylolurea (E234), MDI-based polyurethanes (E235), acrylamido water-soluble polymers (E236), and the molecular dynamics of poly(ethy1 acrylate) and poly (n-butyl acrylate) (E237). Polypropylene was characterized by solid-state IH NMR (E238). Poly@phenylene) and poly(2,5thienylene) were studied by solid-state 13Cand IH NMR (E239). Solid-state 13CCP-MAS NMR was used to characterize differently processed poly(ethy1ene terephthalate) yarns (E24O),polybutadiene, PMMA coreshell latexes (E241), segmented copolymers containing poly(dimethylsi1oxane) (E242), thermotropic polybibenzoates (E243), and polystyrene functionaliied with thiols (E244). A high-temperature melting phase of Xtalline was identified by solid-state 13C CP-MAS NMR (E245). Solid-state I3C CP-MAS NMR was used to quantdy starch in polyethylene (E246), to analyze polymer stabilizers (E247), to monitor the kinetics of polymeric membrane formation (E248), and to characterize haloaldehyde polymers (E249),nylon 7 (E25), polyimides from terephthalaldehyde and aliphatic amines (E251), polypyrrole (E252),and highly conducting polyacetylene (E253). Solid-state 15N NMR was used to investigate the structure of piezoelectric nylon (E254), for the determination of molecular weights of polyaniline samples (E255), to characterize ureaformaldehyde resins (E256),poly (m-xylene-a,a'-diyladipamide), and nylon 6,6 (23257) and to study the cure and degradation of polyimide films (E258). Orientation in aromatic polyesters (E259) and a liquid crystalline side-chain polymer (E260) were characterized by solid-state lH NMR (E259). Solid-state 15N NMR was used to define orientation for uniaxially drawn silk fibers (E261),and orientation in stretched PMMA was determined using solid-state 13C NMR (E262) as it was for hot drawn nylon 6 (E263). Field-cycling NMR relaxation spectroscopy was used to probe the molecular dynamics of poly (di-n-alkylsiloxanes) (E264).A device for the simultaneous measurement of viscosity and orientation by NMR was discussed (E265). The morphology of nylon 13,13 (E266),polyethylene (E267), and polyacrylonitrile (E268) were characterized by solid-state NMR and X-ray diffraction (E266). Solid-state NMR was used to characterize the crystal structure of poly @-phenylene sulfide) (E269),poly(viny1 alcohol) (E270),and syndiotactic polypropylene (E271, E272). A PMMA-poly(viny1idene fluoride) blend was characterized by lH-lgF-I3C NMR triple resonance spectroscopy (E273). SANS and solid-state 2H NMR were used to study the nematic order of 4,4'-dihydroxy-a,a'-dimethylbenzalazine (E274). The liquid crystalline morphology of a rigid-rod polyester from 1,4dialkyl esters of pyromellitic acid and 44-biphenol was investigated by solid-state I3C NMR (E275). Solid-state NMR was used for morphological investigations of phenyl methacrylate, methyl methacrylate copolymers (E276),mica-filled rubber composites (E277),molten poly(ethy1 methacrylate) (E278),PMMA after y-irradiation (E279), and lightly sulfonated polystyrene by 23NaNMR (EZ80). The structure of polyamide fibers was probed by solid-state 15N NMR spectroscopy (E281), and proton spin diffusion coefficients for polybutadiene were determined as a function of temperature (E282). Solid-state proton deuterium polarization transfer NMR was presented as a tool for studying interfaces (23283). Dynamic nuclear polarization was used to enhance 13Csignal at the interface 108R
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of polymer blends (E284).The effects of water on an interfacial silane coupling agent on a silica surface was probed by solid-state 2H NMR (E285) and the effects of water absorbed in a polyimide film were studied by solid-state 13C NMR spectroscopy (E286). Solid-state NMR was used to monitor the polymerization of poly(ether sulfone) (E287)and the reaction of cross-linked PMMA beads with multifunctional amines (E288). Cross-linking in poly(dimethylsiloxane) networks (E289),water-swollen poly(methacry1ic acid) gels (E290),thermally cross-linked polybutadiene (E291), ethylene, vinyl acetate copolymers (E292),vulcanized elastomers (E293,E294),poly(epich1orohydrin) (E295),and urethane crosslinked polyether electrolytes (E296)were characterized by solidstate NMR (E289). The high-temperature NMR free induction decay was modeled to give the distribution of chain lengths between cross-links (E297). The dynamics of the junction point in cross-linked poly(tetrahydr0furan) was characterized by solidstate 31PNMR (E298). Miscibility of polymer blends was investigated by solid-state 2-D NMR methods. Intermolecular interactions in a blend of 1,2polybutadiene and polyisoprene were probed using 2-D nuclear Overhauser effect spectroscopy of samples in the melt (E299). The temperature dependence of the spectral density function for backbone reorientation was probed using 2-D deuterion-exchange NMR (E300). Solid-state 2-D HETCOR NMR spectra were obtained with multipulse line-narrowing techniques, allowing for spin diffusion for a blend of polystyrene-dj with poly(pheny1ene oxide) (E301). A spatially resolved solid-state 2-D NMR experiment was presented (E302) as was a 2-D experiment to eliminate heteronuclear dipolar effects from 13C-detectedproton spectra in wide-line separation NMR spectroscopy (E303). Orientation was studied in polyethylene by rotor-synchronized 2-D 13C CP-MAS NMR (E304), in poly(ethy1ene terephthalate) by multidimensional DECODER NMR spectroscopy (E305), in poly (bphenyleneterephthalamide (E306),and for liquid crystalline side-group polymers (E307). The orientations of methylene group chemical shift tensors were determined for poly(ethy1ene oxide) by separated-local-field NMR (E308). Solid-state 2-D exchange NMR methods were used to characterize molecular dynamics for PMMA (E309),poly(ethy1 methacrylate) (E310),poly(aniline) (E31I), polypropylene, polyisoprene near Tg(E312,E313), and liquid crystalline side-group polymers (E314). A solid-state 3-D exchange NMR method was used to characterize motion in isotactic polypropylene (E315). Dynamics in poly(tetrafluoroethy1ene)were probed using multiple quantum coherences (E316,E31 7), as they were in chloral polycarbonate (E318). A solid-state 2-D NMR spin diffusion method was used to probe local mixing in a blend of poly(2,6dimethylphenylene oxide) with polystyrene-& (E319). A 2-D exchange NMR experiment with isotopic labeling was demonstrated in which conformations in amorphous solid polymers were determined (E320). Solid-state 2-D wide-line separation NMR was used to define the phase dependence of radiation-induced cross-linking in semicrystalline polyolefins (E321). Local packing in polycarbonate was characterized by carbon-deuterium rotational echo doubleresonance NMR (E322). The ring dynamics of poly(bphenyleneterephtha1amide) were characterized using 2HNMR spectroscopy (E323,E324) as were the chain dynamics of poly(styrene-vinyl-&) (E325) and of poly(ethylene oxide) near Tg (E326). The dynamics of styrenevinylpyridine block copolymers absorbed onto silica surfaces were
characterized by 2HNMR spectroscopy (E327) as were long-time dynamics in poly(dimethylsi1oxane) networks (E328) and thermoplastic elastomers based on hydrogen-bonding complexes (E329).The molecular dynamics associated with liquid crystalline polymers were investigated using 2H NMR spectroscopy for thermotropic liquid crystalline polymers (E330), for ternary copolyester liquid crystalline polymers (E331),for several types of liquid crystalline polymers (E332),for side-group polymers with liquid crystalline polymers (E333),for liquid crystalline epoxide thermosets (E334),and for nematic elastomers beyond the critical point (E335). The effect of high pressure on the molecular dynamics of amorphous polyethylene (E336), hydrated Nafion membranes (E337),and polystyrene (E338-E340) was studied by 2H NMR spectroscopy. Proton-deuterium CP-MAS NMR was used to probe blends of PMMA and poly(vinylpheno1) (E341) and a blend of polyisoprene with 1,Zpolybutadiene by 2-D 2H NMR methods (E342). The sequence distribution in deuterated polybutadiene was determined using a 2H-13C INEPT tripleresonance experiment (E343). Chain ordering in uniaxially strained polymer networks was probed by 2H NMR (E344) and for liquid crystal solutions of poly(hexyl isocyanate) (E345) and for perfluorinated ionomer membranes (E346). Rotational diffusion of polystyrene microspheres was investigated by 2H NMR (E347). Solution-state*H NMR was used to investigate cross-linking and branching in acrylate polymer systems (E348). NMR imaging was used to image multicomponent polymeric laminates (E349), elastomers (E350) and swelling kinetics in networks (E351), to spatially resolve rigid polymers and elastomers (E352), to image inhomogeneities in sulfur-cured highvinyl polybutadiene (E353),and to map molecular orientation in solid polymers (E354). NMR imaging was also used to determine temperature distributions in samples using the temperature dependence of the TI (E355) and to determine spatially resolved relaxation parameters which were used to develop material property images (E356). Stress distributionswere imaged in filled polysiloxane under strain (E357). The NMR imaging of y-irradiated cis-l,4polybutadiene was enhanced by swelling the polymer with deuteriobenzene (E358) as it was low-density polyethylene swollen by cyclohexane (E359). NMR magic sandwich echo imaging was applied to solid polymers (E360). Water penetration into nylon 6,6 (E361)and acetone migration into poly(viny1 chloride) (E362) were studied by NMR imaging. Case I1 diffusion was studied in polymeric materials for the purpose of s i m p l i n g its quantification (E363). The diffusion of dioxane in cross-linked polystyrenes was investigated by NMR imaging and solid-state NMR (E364). A one-dimensional NMR method was reported for measuring diffusion utilizing an inversion/recovery magnetic resonance imaging method (E365). A diffusion-ordered 2-D NMR method was described for resolution of molecular size (E366). Pulse field gradient NMR was used to measure the self-diffusion coefficients for ethylene oxide-propylene oxide block copolymers (E367, E368), poly(ethy1ene oxide) (E369), styrene-isoprene block copolymers (E370), poly(dimethylsi1oxane) and poly(ethy1ene oxide) in the melt (E371), and poly(ethy1ene oxide) and poly(siloxanes) in solution (E372), solvent diffusion in PMMA to model film dissolution (E373), interaction of nonionic micelles with a nonionic polymer, ethylhydroxyethyl cellulose (E374),and
the amount of solvent in absorbed polymer layers in concentrated dispersions (E375). The self-diffusion coefficients of water in a swollen cross-linked poly(methacrylic acid) gel were studied (E376),and the microscopic friction in polymer solutions (E377) and motion of swollen spherical microgels (E378) were determined by pulse gradient spin echo methods. THERMAL ANALYSIS
A review of various methods for the assignment of the glass transition temperatures presented 19 papers which detailed what the glass transition is, how to measure it using different techniques, and how the glass transition temperature affects the final end use properties of materials (F1). A recent text reviewed several applications of calorimetry and thermal analysis for characterizing polymer systems. Some of the topics discussed included glass transition, curing of thermosets, gelation, crystallization and melting, polymerization, and coupled techniques (F2). The general application of thermal analysis to characterization of polymers was also reviewed (F3). The fractionation of polypropylene samples using various solvents was examined. In some cases, the solvent fractionated the sample primarily on the basis of molecular weight while for other solvent systems the separation was largely based on tacticity (F4). In another study, the oxidative stability of polypropylene under various processing conditions was studied using thermogravimetric analysis VGA) and DSC. Processing conditions, including both temperature and number of processing steps, were found to have an impact on the overall stability of the material and effect the lifetime expectations of the final part. The use of additives, particularly for use in recycled materials, was also discussed ( F a . The fractionation of polypropylene samples using a Soxhlet extraction method and the subsequent characterization of these fractions by a variety of methods was reported (F6), and the crystallization, melting, and morphology of syndiotactic polypropylene fractions of varying molecular weights were studied (F7). Dynamic mechanical and DSC measurements were used to study the crystallization of polypropylene, high-densitypolyethylene, and blends of the two polymers including discussion of the effects of high-density polyethylene as a nucleating agent (F8). A number of studies investigated the structure and thermal behavior of syndiotactic polypropylene and reported that samples crystallized at low temperature exhibited a double melting point with the higher temperature “normal” melting endotherm being the result of recrystallization during analysis (F9-Fll). In studying the thermal properties of polypropylene fractions, tacticity was found to be the most important parameter affecting crystallinity (F12).The influence of composition on the morphology and crystallinity of blends of isotactic polypropylene and isotactic poly(1-butene) was studied. Changes in the melting endotherm of the polypropylene phase were explained in terms of the miscibility of the two polymers (F13). The effect of fiber reinforcement on the crystallization kinetics of poly(ethy1ene terephthalate) was investigated, and it was found that the crystallization rate is affected by fiber type, crystallization temperature, and the presence of nucleator or plasticizer (F14). The crystallization of polyolefin-nylon 6 blends was also studied by DSC. The volume fraction of the minor component and the compatibility of the two components in the blend were Analytical Chemistry, Vol. 67, No. 12, June 15, 1995
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found to be the major factors affecting crystallization and crystallinity (F15). The crystallization kinetics of poly(pivalo1actone) were studied with notation of differences in crystallization and crystallinity for samples of varying molecular weight (F16). DSC was used to study the crystallization kinetics and to determine the Avrami crystallization parameters for poly(oxymethy1ene) (F17). Polymorphism in poly[bis(p-methoxyphenoxy)phosphazenel was reported. Both a monoclinic and an orthorhombic structure were reported with these forms having different melting temperatures (F18). The thermal behavior of blends of polyamides and ethylenemethacrylic acid copolymer ionomers were studied by DSC, and properties showed a strong dependence on the blend composition (F19). The effects of isothermal crystallization on Nylon 1010 near the melting point and at lower temperatures were reported. Upon melting, crystals formed at lower temperatures recrystallized to the higher melting form, which formed when crystallization occured at temperatures near the melting point (F20). Polymorphic behavior was also reported for the crystallization of syndiotactic polystyrene, and the influence of the solvent used for the crystallization media was discussed (F21). Another study reported similar effects specifically for the syndiotactic polystyrene-decalin system (F22). The melting behavior of ultrahigh modulus and molecular weight polyethylene fibers was studied by DSC and wide-angle X-ray scattering. These fibers were characterized by a double melting point (F23). The effects of annealing on the crystallinity of poly(buty1ene terephthalate) was studied. The presence and growth of a second lower temperature melting endotherm and a corresponding decrease in the main melting endotherm were explained in terms of crystal growth in the amorphous phase with some reorganization of the higher melting crystal structure (F24). The effects of the level of crystallinity of the polypropylene phase on adhesion properties for maleated polypropylene-treated wood surfaces was reported (F25). The thermal properties and cure kinetics for a series of semiinterpenetrating polymer networks were studied (F26'). The thermally induced cross-linking of poly(viny1 chloride) and hydrogenated acrylonitrile-butadiene rubber was studied, and while Tgwas a function of composition, the miscibility of the two polymers was not a function of composition (F27). Differences in the curing of several epoxy systems using both thermal and dielectric curing methods were reported. The dielectric cure gave more rapid curing and a higher Tg after gelation than the thermal cure, although the extent of the differences depended on the epoxy system being studied (F28). A kinetic model for the thermal cure of diethylene glycol bis(ally1 carbonate) was developed including kinetic parameters such as rate constants and activation energy (F29). During studies of the crystallization and formation of thermoreversible gels in mixtures of poly (butylene terephthalate) and epoxy, gel formation was found to be strongly related to the isothermal hold temperature (F30). In a study of the thermal and thermomechanical properties of a graphite-reinforced composite, differences in the processing conditions were found to have major effects on the crystallinity and morphology of the final structure (F31). llOR
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Studying the curing behavior of blends of thermosetting and thermoplastic polyimide resins indicated that the peak temperature for the exotherm increased with increasing levels of the thermoplastic, but the total heat decreased (F32). In a study comparing the relative rates of curing for tetraglycidyldiaminodiphenylmethane and tetraglycidylmethylenebis(o-toluidine), the curing agent used significantly affected both the kinetics of cure and the final properties of the resin (F33). DSC was used to study the kinetics of cure of aryl prop2-vinyl ether-terminated monomer with and without catalyst. While the kinetics were more rapid with catalyst present, the heat of reaction was reduced (F34). The effect of compatibilizers on the nucleation and crystallization of polypropylene/linear low-density polyethylene (LLDPE) blends was studied (F35), and in a blend of atactic poly(viny1 alcohol) with a mostly syndiotactic poly(viny1 alcohol), the two forms were found to cocrystallize (F369. The effects of blending polymers on the relative stability of the polymer versus the stability of the individual polymers were studied. It was reported that for some polymer systems thermal stability was actually increased while for other cases no effect was observed (F37). The miscibility and phase separation in poly(methyl methacrylate) -poly(vinyl chloride) blends was studied, and for solution-blended samples, a shift in Tg and a heat of demixing were observed upon heating (F38). A review of thermal/mechanical degradation of polymer blends reported that interaction among the components present either increased the degradation rate or decreased the degradation rate by the formation of compounds that stabilized the blend (F39). The relationship between sheer and degradation for vinylidene chloride copolymers was demonstrated (F40). Chemiluminescence was used to study the degradation of polyamide 8 (F41). The use of an oxygen uptake measurement for studying the photostability and thermal stability of polyethylene was reviewed (F42). A method was presented to derive the kinetic equations for polymer degradation by studying the elimination of low molecular weight compounds (F43). The thermal degradation of partially para-brominated polystyrenes showed that the primary products formed were the monomers, with some dimer and trimers also being formed (F44). The relationship between polymer degradation, which produces fuel, and flammability was reviewed for common commercial polymer systems (F45). In another review article, the relationship between polymer structure and flammability was discussed as well as methods for preparing thermally stable polymers (F46). A study of the thermal/mechanical degradation of linear polyethylenes indicated that increased levels of branching affected the rate of degradation. Because the level of branching was directly correlated to the type of catalyst used, the degradation of these polyethylene samples was likewise correlated to the catalyst used (F47). Derivative TGA was developed as a method for identifying and quantifying elastomers and processing oils in tire rubber (F48). Thermomechanical analysis (TMA) was used to characterize cellular EPDM rubber materials (F49), and dynamic mechanical analysis @MA) was used to study the interaction of fillers with rubber host systems. Aging was not found to affect these interactions, but heat treatment did have a profound effect on material properties (F50). The use of TGA to study vulcanized
rubber systems was reviewed (F51),and a new method using an autostepwise TGA was described for characterizing elastomeric materials (F52). DMA was used to study adhesion between poly(viny1 chloride) and nitrile rubber sheets. Contact time and temperature were found to be important parameters to allow interdiffusion of polymer chains across the interface (F53). DMA was also used to study the chemical resistance of several elastomers toward naval fuels (F54). DSC was used to study the curing kinetics of epoxy-polyester powder coatings using different accelerators and the thermal degradation of the final product (F55). An instrument was described for simultaneous chemiluminescence and DSC and the application of this instrument to study the glass transition and oxidative stability of poly(N-vinyl-2pyrolidone) (F56). Dielectric heating of polymer systems is becoming a more widely applied method of polymer processing, and the response of various polymers to microwave processing was studied (F57). Use of lower frequency measurements was also discussed as a method of predicting high-frequency response. As part of a study on microwave heating, the dielectric behavior of glassy amorphous polymers at 2.45 GHz was studied (F58). A review of the analysis of dielectric relaxations in polymer systems included review of mathematical models with applications to polymer blend systems (F59). The dynamics of molecular motions of Bisphenol A polycarbonate were studied using dielectric spectroscopy, neutron scattering, and mechanical relaxation. The study demonstrated the relationships between the various molecular motions and polymer transitions (F60). The crystallization of poly(ethy1ene terephthalate) was also studied using dielectric measurements. Results were discussed in terms of a two phase amorphous systems (bulk and crystal interface), and deviations from the model were considered in terms of an ordering of the bulk amorphous phase during crystallization (F61, F62). Dielectric relaxation measurements were used to study the relaxation of entangled h e a r cispolyisoprenes (F63). The relationship between main-chain and normal-mode relaxations for poly(propy1ene oxide) was studied using dielectric methods (F64). Dielectric measurements were applied to the study of the relaxation of nonlinear optical (NLO) polymer systems and the reorientation of dipoles related to the loss of NLO activity (F65). A review of the relationship between polymer relaxations, including liquid crystal relaxations, and dielectric measurements was presented (F66). The effect of increased levels of cross-linking on the molecular relaxation of amorphous copolymers as studied by dielectric measurements was reported and related to various relaxation models (F67). A comparison of dielectric relaxations for different Bisphenol A polyarylates was reported (F68). Water sorption in epoxy-based materials was characterized using dielectric spectroscopy (F69). The dielectric relaxation of isotactic polystyrene at temperatures between the glass transition temperature and the melting point was studied, and these relaxations were found to be dependent on the level of crystallinity in the system (F70). Studies of the effect of humidity on the dielectric response of thin (75 pm) films indicated that dielectric loss factors increased with exposure to higher levels of humidity (F71).
Thermally stimulated depolarization current (ED) was applied to characterize aging in polymers used for outdoor high-voltage insulation (F72). The dielectric breakdown of poly(vinylidene fluoride) was studied. The ferroelectric and piezoelectric properties were used to explain the lower breakdown strengths for this polymer as compared to other polymers not having these properties (F73). An increase in dc conductivity with increasing crystallinity was observed for samples of Nylon-12 (F74). The effects of thermal resistance in characterizing the apparent melting behavior of polymers systems was studied. Multiple melting peaks for indium samples sandwiched between various numbers of layers of polyethylene were observed, and samples with the least number of polyethylene layers between the indium and the sensor had the lowest melting point. The melting point increased with increasing numbers of polyethylene layers (F75). The thermodynamics of polymerization for copolymer systems were reviewed (F76). The application of thermal analysis methods to study thin polymer films, such as those used in the microelectronics industry, was reviewed (F77). The effects of pressure, temperature, and time on the glass transition of polymers systems, studied using pressure/volume/ temperature (WT) measurements, were reviewed (F78). A review of the application of thermal analysis for studying various transitions (such as Tg)in polymer systems included relationships between molecular segments and transition temperatures (F79). A method for simultaneous DSC/near-infrared analysis, and the application of this method to study the cure of an epoxy system, was discussed (F80). The application of thermal analysis for the characterization of recycled polymers was discussed (F81). The determination of the refractive index and birefringence of a thin (3.7 pm) polyimide film as a function of temperature and humidity was performed using a prism coupling method and subsequently related to the determination of the volumetric expansion of the thin film (F82). The study of poled nonlinear optical polymers discussed the observed relaxation rates in terms of nonequilibrium free volume of the sample (F83). The thermal stability of fiber-optic sheathing materials was studied using DSC, TGA and laser ablation. The results indicated that the degradation products played the largest role in the loss of resistive properties. Silicon-based sheathing materials performed better than carbon-based materials because they did not form carbon-based products upon degradation (F84). The application of enthalpy relaxation to probe the thermal history of an interpenetrating polymer network was examined. The observed heat capacity changes were discussed in terms of a distribution of relaxation times within the network (F85). A method was developed for measuring macromolecular entanglements using a method referred to as swelling differential scanning calorimetry (F86). DSC and dynamic mechanical analysis were used in conjunction with lap shear strength testing to relate the degree of cure with the buildup of mechanical strength in toughened epoxy adhesives (F87). The effect of loading short poly(ethy1ene terephthalate) fibers into styrenic block copolymers was studied. The use of a bonding agent to link the fiber and the matrix was found to be the most critical parameter in obtaining good part strength (F88). Thermomechanical analysis was used to study the shrinkage of PET films and study the correlation with the observed shrinkage in commercial containers (F89). Analytical Chemistry, Vol. 67, No. 12, June 15, 1995
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Differential scanning calorimetry was used to study the thermal characteristics of tetrduoroethylene-peduoroalkyl vinyl ether copolymers. A low-temperature transition was observed for the copolymer containing up to 4% of the peduoroalkyl vinyl ether at temperatures between -20 and 20 "C, while the peak melting of tetrafluoroethylene at temperatures of about 310 "C and lower were observed with up to 10%of comonomer. It was suggested that there is at least partial exclusion of the side chain of the comonomer (F90). The application of enthalpy relaxation determinations to study the miscibility of multicomponent systems was determined to be a useful method for describing the extent of miscibility for a blend system (F91). Cone calorimetry was used to study the combustion behavior of polyurethane flexible foams. Under these test conditions, differences in the flexible foams found in small-scale testing were no longer observed. Other factors, in particular foam density, were found to be important in studying foam flammability (F92). The thermal behavior of poly(pheny1ene sulfide) and some of its derivatives was studied (F93), and the relaxation of oriented liquid crystalline polymers was studied using a combination of techniques. Three relaxation processes were observed during this study (F94). DSC and TGA were used to predict the effectiveness of using unsaturated dicarboxylic acid systems in durable press finishing systems (F95). Vicinal water structure around negatively charged polystyrene latex was studied using TGA and differential thermal analysis (F96). Studies of the thermal expansion behavior of thermoplastic composites indicated that heating these materials above the glass transition temperature resulted in an irreversible change in polymer properties (F97). Workers studying the reaction of ozone with polyethylene pulp fibers observed a gradual change in thermal properties (as measured by DSC) for several hours. A dramatic change occurred at a time that corresponded to the reaction reaching into the bulk of the fiber (F98). The miscibility of a polyarylate with a liquid crystalline copolyester was studied, and two glass transitions were observed over the range of 10-90 wt %. This suggested only partial miscibility of the two polymers (F99). Thermomechanical analysis was applied to study the linear coefficient of thermal expansion and the determination of the glass transition temperature of a segmented rigid-rod polyimide film (FIOO). While DSC is frequently used to determine crystallinity in polymers, recent work on poly(ary1 ether ether ketone) indicated that heating resulted in a recrystallization process. Consequently, accurate determination of the level of crystallinity that existed in the sample before heating was not possible (FIO1). DSC, wide-angle X-ray diffraction, and dynamic mechanical analysis were used to study phases in blends of nylon 6 and poly(acrylic acid) cast from aqueous formic acid solutions. At concentrations of greater than 50%poly(acry1ic acid), no melting endotherm was observed and only a single Tgwas found, which suggested miscibility and a single phase (F102). TGA was also used to determine the diffusion coefficient of water in polymer films where weight gain versus time was used to calculate the diffusion coefficient (F103). Electrical impedance spectroscopy was used to study water diffusion in poly(ethy1ene 112R
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terephthalate) films (F104),and the effects of aging on the thermal properties of ethylene-propylene-diene-monomer (EPDM) roofing materials were studied (F105). TGA was used to study the effects of composite construction on the oxidative degradation of these samples. The orientation of the various layers appeared to play an important role in the oxidative process by affecting the rate of oxygen diffusion into the sample (F106). INCRAREDANDRAMANSPECTROSCOPY Infrared spectroscopy continued to be an invaluable tool for the analytical study of polymer cross-linking and degradation, morphology, surface chemistry, and copolymer composition and the general characterization of macromolecular systems. A tremendous increase was observed in the use of both Fourier transform and conventional Raman spectroscopies in the characterization of polymers during the time period covered by this review. Raman spectroscopy has become a routine analytical tool for characterization of polymeric systems. Near-infrared spectroscopy continued to be of importance, especially for quantitative analysis and on-line applications. Many excellent reviews and overviews of the application of these vibrational spectroscopic techniques to polymer characterization were published during the time period covered by this review article. These are outlined in the following paragraphs followed by a discussion of papers dealing with specific polymer systems. A comparison of the mid-IR to the near-IR with application to polymers, fibers, and coatings was published (GI). A thesis dealing with the use of infrared spectroscopy to study cross-linking and surface reactions in macromolecules was presented (G2). Reviews of the use of stepscan infrared spectroscopy, a tool for obtaining time- and phase-resolved vibrational spectra, demonstrated the versatility and potential of this technique (G3, G4). Depth-profiling using stepscan infrared photoacoustic spectroscopy was also discussed (G5). A thesis studying chemical reactions at polymer/substrate interfaces using infrared and X-ray photoelectron spectroscopies was presented (G6). The advantages of the use of infrared spectroscopy in an industrial laboratory were reviewed, with particular emphasis on surface anaIysis and microspectroscopy (G7). Potential applications of diffuse reflectance infrared spectroscopy in the characterization of advanced materials were discussed (G8). Application of optical theory to the study of thin films and surfaces was presented (G9). The application of the infrared microscope to forensic analysis was reviewed (G10). The interface of thermal gravimetric analysis and infrared spectroscopy was discussed (GII). The complementary role of infrared and Raman spectroscopy in the characterization of polymers was presented in a review with 325 references (G12). The application of near-IR spectroscopy to the petroleum industry was discussed (GI3). The application of Raman spectroscopy to the study of polymers and polymerization processes was discussed in various reviews (G14, G15). The use of Raman microscopy in the study of structure and mechanics of fibers and composites was discussed (G16). Phase structure and composition determination using Raman microscopy of polymer blends were described (G17), and progress in the use of Raman spectroscopy in the characterization of biodegradable polymers was reviewed (G18). The characterization of interfaces in polymers and composites by Raman spectroscopy was reviewed with 51 references (GI9),and a thesis
was also published in this area (G20). The application of the Raman microscope to the study of orientation, stress, and strain in these materials was presented (G21), and Raman spectroscopy of polyconjugated organic oligomers and polymers was reviewed (G22).
Transient infrared spectroscopy techniques were presented for the on-line analysis of solids and viscous liquids, such as a polymer extruder melt stream (G23). Spectroscopic approaches were discussed for analysis of nonequilibrium processes in polymers using infrared photoacoustic spectroscopy (G24). Analysis of common errors that occur when polymer orientation functions were calculated from infrared dichroism measurements was presented (G25). The development of an automated system for the interpretation of infrared spectra of polymers was described ( G 2 6 4 2 8 ) . Prediction of orientation gradients at polymer surfaces using variable-angle attenuated total reflectance (ATR) infrared spectroscopy was discussed ((29). The resolution of polymer spectroscopic data was presented using discriminant and eigenvalue analysis (G30). Quantitative determination of crystallinity and the effect of orientation on the morphology of high-density polyethylene (HDPE) were determined by Raman and NMR spectroscopies (G31, G32). Changes in morphology during melting and annealing of high molecular weight polyethylene were observed by Raman spectroscopy (G33). Raman band width, shape, and frequency changes were used to characterize pretransitional processes in polyethylene (PE) (G34). Information about the structure of weld lines in PE was obtained using low-frequency Raman spectroscopy (G35). Evidence was presented for the presence of twistons in the IR and Raman spectra of PE (G36). Raman spectroscopy was combined with DSC and X-ray diffraction (XRD) to study crystallinity and morphology of polyethylene oligomers (G37). The origin of the outstanding damage tolerance of ultrastrong PE fibers was explored by Raman spectroscopy (G38),and phase structure of drawn HDPE fiber was investigated with Raman spectroscopy (G39). Molecular deformation in highperformance gel-spun PE fibers was studied using the symmetric C-C stretching Raman band near 1128 cm-1 (G40). The distribution of molecular orientation in thick PE samples was studied by Raman spectroscopy and infrared dichroism (G41), and orientational order in PE foils was studied by polarized Raman spectroscopy (G42). The early stages of ethylene polymerization were studied by infrared spectroscopy using deuterated ethylene monomers (G43). An infrared method was presented for determining crystallinephase orientation in polyethylene films (G44). Conformational change in PE during annealing or deformation was studied by infrared spectroscopy (G45). Short-chain branching in PE was characterized by using the methyl and methylene rocking bands of the infrared, yielding a procedure less costly and faster than the more traditional NMR technique (G46). The relationship between stress-induced vibrational frequency shifts and deformation mechanism of polyethylene chains was explored using infrared and Raman spectroscopies (G47). The crystalline/ amorphous content on PE surfaces was measured using ATR infrared spectroscopy (G48). Infrared dichroism of G°Co-irradiated low-densitypolyethylene (LDPE) was used to study the relaxation of taut tie molecules during annealing (G49). Near-infrared spectroscopy was used to determine the blend ratio of HDPE and LDPE in extruded films (G50).
Infrared spectral changes were associated with the cocrystallization and phase segregation of deuterated HDPE and linear LDPE (G51). The simultaneous characterization of molecular weight, molecular weight distribution, and chemical composition (as a function of molecular weight) of ethylene-based polyoleh copolymers was made by coupling a high-temperature gel permeation chromatography instrument with an infrared spectrophotometer (G52, G53). Grazing-angle reflection/absorption spectroscopy was used to study the interaction between adhesion promoters and polymer surface of polyolefins (G54).The formation of interchain bridges of unsaturated double bonds in the amorphous phase when PE was irradiated in the presence of polyacetylene was substantiated by infrared spectroscopy (G55). Local structural changes in the zinc salt of an ethylenemethacrylic acid ionomer upon water absorption were monitored by observing changes in the carboxylate antisymmetric stretch region of the IR spectrum (G56). The amount of crystallinity at weld lines in PE and polypropylene (PP) was determined with infrared microspectroscopy (G57) while optical birefringence and IR dichroism were used to measure molecular orientation in isotactic PP disks ((258). Photooxidation and thermal oxidation of nonwoven PP fabric were studied by infrared photoacoustic spectroscopy (G59), and additive levels in PP pellets were determined using near-IR spectroscopy (G60). Residual stresses in PP fibers were monitored by infrared spectroscopy and correlated to draw ratio and polydispersity (G61). Photooxidation of polypropylene fibers was analyzed using infrared photoacoustic spectroscopy and infrared microspectroscopy (G62). ATR was used to examine the grafting of polypropylene films by poly (acrylic acid) (G63). Infrared procedures for determining the surface composition and order of PP/EPDM rubber blends were developed using ATR spectroscopy (G64). Peroxide vulcanization processes in ethylene-propylene -monomer systems were studied using infrared spectroscopy (G65). Special reference to the analysis of polybutadiene and its copolymers was contained in a review dealing with the analysis of synthetic rubbers by infrared spectroscopy (G66). Partitioning of acrylonitrile between polymer and aqueous phase of a butadiene rubber latex was studied by Raman spectroscopy (G67). Polybutadiene microstructure and comonomer composition of several butadiene-acrylonitrile copolymers were determined using Raman spectroscopy (G68). A Fourier transform Raman spectrometer as a detector was used for the analysis of polybutadienes with varying cis-1,4, truns-1,4 and vinyl-l,2-contents (G69). Thermal degradation of polybutadiene was assessed using infrared and NMR spectroscopies (G70). The microstructure of hydrogenated polybutadienes during hydrogenation and hydrobromination reactions was examined using Raman spectroscopy (G71). Gas-phase infrared and mass spectroscopy were used to identify the pyrolyzate from polyfiutadiene sulfone) prepared by %o y-radiation (G72).
Crystallization of truns-l,4polyisoprene from the melt, monitored with infrared spectroscopy,resulted in discussions regarding lamellar morphology (G73). Infrared spectra of synthetic polyisoprenes were presented, including discussion regarding improvements in the determination of microstructure (G74). Infrared dichroism was used to investigate chain orientation in networks of polyisoprene and styrene-isoprene copolymer (G75). Relaxation and orientation behavior of polyisoprene-poly (vinylethylene) mixtures were correlated with infrared dichroism Analytical Chemistry, Vol. 67, No. 72,June 15, 7995
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measurements (G76). Conjugation length in diblock copolymers of acetylene and norbornene was determined using Raman spectroscopy (G77). A thesis described the determination of diffusion coefficients in poly(dimethylsi1oxane) (PDMS) by infrared spectroscopy (G78). Infrared dichroism was used to investigate segmental orientation in PDMS (G79, G80). The nondestructive identification of silicone coatings on eyeglass lenses was conducted using ATR spectroscopy (G81). Rheooptical infrared spectroscopy was used to monitor orientation and strain-induced conformational regularity in PDMS during cyclic elongation and recovery (G82). Diffusion coefficients of alcohols in PDMS were measured (G83) while diffusion of urea in PDMS, determined using ATR agreed with data from bulk transport methods (G84). Raman spectroscopy and thermal analysis were used to study the crystallization of high and low molecular weight cyclic PDMS (G85). Quantitative analysis of the SiH groups on PDMS surfaces was performed using ATR (G86). Infrared and electron spectroscopies were used to study the surface segregation of PDMS in styrene-dimethylsiloxane block copolymers (G87). Polarization modulation infrared spectroscopy was used to measure molecular orientation in stretched films of PDMS (G88). Differences in the polarized Raman spectra of cocondensation products of y-substituted propyltrialkoxysilanes were compared (G89). The oxidation of poly(methylsi1ane) and subsequent transformation into poly(carbosi1ane) on silicon wafers were monitored by infrared spectroscopy (G90). The kinetics of the anionic solution polymerization of polystyrene was monitored using near-infrared spectroscopy (G91). Fiber-optic Raman spectroscopy was used to monitor the in situ emulsion polymerization of polystyrene (G92). Polarized infrared spectroscopy was used to study molecular orientation in optical fibers of PS (G93). The effect of particle size on the diffuse reflectance spectra of polystyrene spheres was discussed (G94). Gelation and crystallization of atactic and isotactic solutions of PS in carbon disulfide were monitored by infrared spectroscopy (G95). The conformation ordering that occurs during the gelation of syndiotactic polystyrene in various organic solvents was monitored using infrared spectroscopy (G96). Surface-enhanced Raman spectroscopy was used to probe diffusion processes during the swelling of PS in n-hexane (G97). Rheooptical infrared spectroscopy was used to analyze orientational relaxation in polystyrene (G98). Two-dimensional infrared spectroscopy was used to probe the submolecular dynamics of atactic PS (G99, G100, G101). The interdiffusion of PS and deuterated polystyrene was investigated using surface-enhanced Raman spectroscopy (G102-GI04). Characterization of polystyrene and poly(methy1 methacrylate) composition distribution was performed using an HPLC coupled to an infrared spectrophotometer via a solvent evaporation interface (G105). Interdiffusion in PS and poly(viny1 methyl ether) was studied using ATR (G106,G107) as well as light scattering combined with transmission infrared spectroscopy (G108). Infrared spectra and chain conformations of crystalline syndiotactic poly (P-methylstyrene) were presented in another study (G109). Infrared studies of the photooxidation of styrene-acrylonitrile copolymers were discussed (G110, G111), and dynamic infrared dichroism spectroscopy was used to characterize the orientation of deuteriumlabeled styrene-isoprene copolymers in the solid state (G112). 114R
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Infrared spectroscopy was used in the study of crystallinity of vinylidene chloride copolymer coatings (G113) and the determination of plasticizer migration from poly(viny1 chloride) (G114, G115). Thermal degradation of polyurethane-backed PVC was studied by Raman microline focus spectrometry (G116). In situ Raman spectroscopy was used to investigate the thermal degradation of PVC (G117). The infrared spectra of poly(vinylidene fluoride) O F ) films under the influence of an electric field were explained with the concomitant structural changes induced by the field (G118,G119). Oriented PVDF films were characterized by ATR spectroscopy (G120),and the diffusion of ethyl acetate in PVDF as a function of crystallinity was measured using infrared photoacoustic spectroscopy (G121, G122). Raman microspectroscopy was used to map the crystalline-phase transition produced after microindentation of PVDF (G123). The transition front in the neck between the isotropic and oriented regions in uniaxially stretched PVDF and PP systems was analyzed using Raman microspectroscopy (G124). The relationship between infrared and Raman spectra of alternating ethylene-tetrafluoroethylene copolymers and electronic mobility in these molecules was discussed (G125). Specular reflectance and photoacoustic sampling methods were compared for infrared spectroscopy of nylon 6,6 (G126). Hydrogen bonding in a series of polyamides was studied by Raman spectroscopy (G127). Raman spectra of commercially available nylons were obtained in an attempt to obtain quantitative information about hydrogen bonding and secondary structure (G128, G129). Near-infrared spectroscopy was used to provide a rapid, nondestructive procedure to identify the various layers of nylon/ polyethylene food packaging laminates (G130). Hydrogen bonding of polyacrylamide in D20 was monitored by Raman spectroscopy (G131). A study of the relationship between the level of cross-linking and free and hydrogen-bonded water in cross-linked polyacrylamide gels was conducted using Raman spectroscopy (G132). Another study established the feasibility of using Raman spectroscopy to quantdy levels of melamine and melamine cyanurate in nylons (G133). Infrared photoacoustic spectroscopy and differential scanning calorimetry were used to examine the structural changes that occurred upon annealing of injection-molded nylon 6,6 (G134). Vibrational spectra of poly(pphenyleneterephtha1amide) crystals were calculated using molecular dynamics resulting in correlation of lowfrequency bands with hydrogen-bonding interactions (G135). Another study explored factors that affect the quantitative measurement of polyimide films (G136). The curing reaction of a polyimide bonding agent was monitored using Raman spectroscopy (G137), and ion-beam-induced structural transformation in an aromatic polyimide film was evaluated by infrared spectroscopy (G138). Other workers discussed the effect of W irradiation on polyimide films and proposed a mechanism for the resultant change in chemical structure (G139). The thermooxidative degradation of polybenzimidazole and a polybenzimidazole/poly(ether imide) blend was investigated with infrared spectroscopy (G140). Near-infrared spectroscopy was used to monitor the production of polyurethane (G141). The structure and deformation behavior of poly(ether urethane) elastomers was investigated by infrared spectroscopy (G142). The urethane group association scheme in poly(ether urethanes) was described by the amide I infrared absorption band contours (G143). Phase behavior of mixtures
of a model urethane with polyether macroglycols (G144) and the equilibrium association of urethane groups in poly(ether urethanes) were studied by infrared spectroscopy (G145). Extractables from poly(ether urethane urea) elastomers were also identified by infrared spectroscopy (G146). The influence of temperature and styrene solvent on hydrogen bonding in amorphous linear aromatic polyurethanes was investigated by infrared spectroscopy (G147, G148). Raman spectroscopy was used to characterize the behavior of a diacetylene-containing urethane copolymer under tensile and compressive strain (G149). The interface between a urethane paint and partially hydrolyzed ester copolymer was studied with infrared microspectroscopy (G150). The cell membranes in a flexible polyurethane foam were studied with infrared microspectroscopy (G151). The effect of the wedging error in quantitative analysis of polyurethane foams was described (G152). Mid-infrared transmitting optical fibers were used to monitor the cure process of a polyurethane foam (G153). Infrared microspectroscopy was used to characterize acrylic fibers for forensic analysis (G154). Poly(methy1 methacrylate)/ poly(viny1 alcohol) laminates were characterized by obtaining ATR spectra at varying incident angles to profile the depth of the laminate (G155). Differential scanning calorimetry and infrared spectroscopy were combined to provide correlation between melt temperature and composition (G156). Surfactant migration in acrylate copolymer coatings was monitored using ATR (G157), and Raman spectroscopy was used to monitor the emulsion polymerization of acrylate latexes (G158, G159). Other workers discussed quantitative analysis of methacrylate copolymers and the advantages and disadvantages of cast films and solutions (G160). A nondestructive method for the determination of residual monomer in poly(methy1 methacrylate) was developed using Raman spectroscopy (G161). A discussion of the interpretation of low-frequency Raman spectra of poly(methy1 methacrylate) was presented (G162), and miscibility and interactions in poly (hydroxy methacrylate) -poly (vinylpyridine) blends were studied by infrared spectroscopy (G163). The kinetics of the photoinduced anionic polymerization of ethyl cyanoacrylate was monitored with infrared spectroscopy (G164). Infrared spectroscopy was used to investigate the effect of cross-linking agents on the molecular properties of the acrylic resins used as denture base materials (G165). The interaction between ethylene(viny1 acetate) copolymer and polyethylene was evaluated using infrared spectroscopy (G166). Infrared emission spectra of poly(viny1 acetate) was obtained after enhancement by the island structure of gold (G167). Nearinfrared diffuse reflectance was used to measure poly(viny1 alcohol) size on warp yarns (G168). Changes in the Raman spectra of solutions of ethylene-vinyl alcohol copolymer and poly(vinyl alcohol) were related to crystallinity, stereochemistry and partial deuteration (G169). Thermal degradation of ethylene(viny1 acetate) copolymer films was studied by infrared spectroscopy (G170). A dissertation described the use of vibrational spectroscopy to study the conformation and dynamics of poly(acry1ic acid) as a function of ionization (G171). Hydrogen bonding in the zinc ionomer of poly(ethy1ene-co-methacrylicacid) was studied by infrared spectroscopy (GI 72), and ion solvation and association in polymer electrolytes was studied by Raman spectroscopy (G173). The role of the cyclic anhydride as the intermediate in the ester cross-linking of cotton cellulose by poly(carboxylic acids)
(GI 74) and the characterization of polyanhydrides (GI 75) were investigated using infrared spectroscopy. The linear oligomers of poly(oxymethy1ene) with acetyloxy end groups were characterized with infrared and Raman spectroscopy (GI 76). The thermal degradation of ethylene-propylene-carbon monoxide copolymers was investigated by infrared spectroscopy (G177), which was also used to determine the average number of oxyethylene groups and molecular mass in poly(ethy1ene glycol ether)s (G178). The miscibility of poly(2-chlorostyrene) and poly(vinyl methyl ether) was also characterized by infrared spectroscopy (GI 79). The role of vibrational spectroscopy in the study of crystallinity in poly(ary1 ether ether ketone) (PEEK) films was discussed (G180) while other workers compared univariate and partial leastsquares approaches to the measurement of crystallinity in PEEK using Raman spectroscopy (G181). Infrared dichroism, birefringence, and shrinkage stress measurements during tensile drawing of PEEK were correlated in a series of experiments (G182). The development of orientation in uniaxially drawn PEEK was o b served with infrared spectroscopy (G183). The crystallization process in blends of PEEK and poly(ether imide) was studied using Raman spectroscopy (GI84 and thermal degradation in PEEK (G185) and PEEK-carbon composites was investigated using infrared spectroscopy (G186). The shift of the hydroxyl band in the near-infrared spectrum of polyesters was discussed as an indicator for the progress of the esterifcation reaction (G187). Polarized internal reflectance spectroscopy was used to evaluate molecular orientation and crystallinity of poly(ethy1ene terephthalate) (PET) film surfaces (G188). Transmission spectroscopy was compared to ATR for the determination of crystallinity in PET films (G189). Molecular changes upon stretching of PET yarns were measured with rheooptical infrared spectroscopy (G190) while infrared and Raman spectroscopy were used for rheooptical studies of the bidirectional drawing of PET (G191). Infrared photoacoustic spectroscopy was used to study structural changes in glass fiberreinforced PET after compression molding and annealing (G192, G193). The degradation of glass fiber-reinforced polyesters via hydrolysis was investigated with infrared spectroscopy (G194). Infrared photoacoustic spectroscopy and diflerential scanning calorimetry results were used to study differences in the skin and core of injection-molded PET (G195). Infrared depth profiling was used to study recrystallization in laser-amorphized PET (G196), and conformational changes during annealing of PET were studied using Raman spectroscopy (G197). A kinetic analysis of the thermal decomposition of PET and polyfiutylene terephthalate) (PBT) was obtained using thermogravimetric analysis coupled with infrared spectroscopy (G198, G199). Photolysis products of PBT were identitied by infrared spectroscopy (G200, G201). Structure/property relationships in partially sulfonated PET were also investigated using infrared spectroscopy (G202). Compatibility of blends of poly(ethy1 acrylate-co-4vinylpyridine) with zinc-neutralized sulfonated PET was studied with infrared spectroscopy (G203). An (isodecyl end-capped) propylenediol adipate polyester was analyzed using liquid chromatography coupled with infrared spectroscopy (G204). Biomedical poly (orthoesters) were analyzed for diol content and methylene number by Raman spectroscopy (G205). Near-infrared and mid-infrared techniques were Analytical Chemistry, Vol. 67,No. 12, June 15, 1995
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compared for the determination of hydroxyl number in polyesters (G206).
The structure of polycarbonate after irradiation by protons and lithium ions was studied by infrared spectroscopy (G207). The physical and chemical interactions among the components of a highly cross-linked epoxy resin toughened with Bisphenol A polycarbonate were investigated by infrared spectroscopy (G208). Near-infrared spectroscopy was used to quantitatively analyze the cure reaction of digylcidyl ether of Bisphenol A (DGEBA) epoxy resins cured with diamino diphenyl sulfone hardener (G209). The effect of water absorption by a filled DGEBA epoxy resin on its mechanical properties was studied by infrared spectroscopy (G210) while infrared and NMR spectroscopies were used to characterize epoxy networks based on DGEBA and butanediol (G211). Infrared reflectance microspectroscopy was used to examine compositional differences across the interface of an epoxy adhesive film on treated aluminum (G212). Anaerobic adhesive cure in thin and thick bond-line situations was characterized using ATR spectroscopy (G213). A review presented the application of Raman spectroscopy to study the deformation mechanics of aramid fibers in epoxy resin matrices (G214, G215). Another review included the application of vibrational spectroscopy to study of the dynamics in liquid crystalline polymers (G216). A thesis described use of dynamic infrared spectroscopy to study liquid crystals and polymer films (G217). Infrared dichroism was used to investigate orientation in a thermotropic main-chain copolyester (G218). Conformation, ordering, and mobility in thermotropic liquid crystalline polymers (LCPs) were studied by infrared and NMR spectroscopies (G219). Molecular orientation in flat plates of LCPs (G220) and a comparison of the polymer and liquid crystal droplet regions in polymer-dispersed liquid crystal films were made using infrared microspectroscopy (G221). The orientation distribution of LCP sheets was studied by infrared dichroism and ATR spectroscopy (GZZZ), and mechanically induced orientation in thin films of side-chain U P S was evaluated using infrared dichroism (G223). A side-chain polyacrylate LCP was also characterized by infrared spectroscopy (G224). The temperature dependence of the infrared dichroism of a phenyl benzoate side-chain polymeric liquid crystal was investigated (G225), and the structures of a series of laterally attached sidechain liquid crystalline polysiloxanes were characterized by infrared dichroism and X-ray difh-action (G226). The dynamic behavior of a polymer-dispersed liquid crystal under an electric field was studied by infrared spectroscopy (G227). Dipole/dipole interactions in liquid crystal polyesters were investigated by monitoring the C=O stretching frequency in the infrared (G228). The growth morphology of electrochemically grown polythiophene films was monitored using infrared dichroism (G229, G230) with infrared and Raman spectroscopies (G231). The extent of cure of benzocyclobutene thin films was evaluated by infrared spectroscopy in order to determine the feasibility of rapid thermal cure of these materials using an infrared belt furnace (G232, G233). Infrared dichroism was also used to assess the orientation in poly(ary1enevinylene) copolymers and blends (G234. The chemical structure of electrically conducting polypyrrole films was studied using Raman spectroscopy (G235). Cooperative motion of rigid groups in the semicrystalline azobenzene polymers used for reversible optical storage applications was characterized using infrared dichroism (G236). Orientation of uniaxially drawn 116R
Analytical Chemistry, Vol. 67, No. 12, June 15, 1995
poly(acrylonitri1e films) was also characterized using infrared dichroism (G237). The effect of heat treatment on phenolformaldehyde resins was characterized by Raman spectroscopy (G238), and infrared dichroism was used to study the orientation of uniaxially stretched films of poly(vinylpheno1) (G239). Charles G. Smith recent1 retired after 28 years with the Analytical
Sciences Laboratory, Dow Ciemical, U.S.A., Midland,,MI. He received his B.S. degree from Alleghen College and has M.S. in chemzstry from the Universit of Michigan. joined Dow in 196% After four years of method devei ment in the Organic and ricultural Products Groups, has concentrated on as he transferre1 to the Plastics Grou . chromatographic separations and appecations to polymeric systems. h e past 16 years were devoted to developin p rolysis techniques for polymer analysis. He is author or coauthor of5dpublications and one patent and chairman ofASTMD20.70 Subcommittee on Analytical Methods for Plastics.
d
%
Patrick B. Smith is a member of the Spectrosco y Group of the Midland, MI. Analytical Sciences Laborato Dow Chemical. He received a Ph.D. in physica?ihemzstryfiom dichz an State Unzverszty in 1978. His research interests are largely concern, with the structural characteritatton of spthetic polymers. by. NMR spectroscopy, both, in solution and zn the solid state. Dr. Smzth as coauthor of 34 publzcatzons and 1 patent, and he has lectured on the !ubject of olymer characterization by NMR !pectroscopy.. He is an Adjunct ProLssor of C h e m s t y at Cenfral Michzgan Unzverszt. and a member of The Ameracan, Chemacal Soczety. He recezved the d d l a n d Chapter Sagma Xz award an 1987.
lJ.S.1, f
Andrew J. Pasztor, Jr., j s a Research Associate in the Thermal Analysts Group of the Analyttcal Scaences Laboratory, Dow Chemacal, U.S.A., .Midland, @I. He recejved his Ph.D. in thysical chemistry fiom The Unzverstty ofMzamz (Florzda) zn 1976. Heloaned Dow and worked in the Halo ens Research Laboratory and the Styrene Molding Polymers LaboratoY%efore taking his current assignment. His current research interests include olymer degradation, curing of thermoset resins, and application of diekctric s ectrosco y to polymer systems. His is a member of the North American A e n n a l i n a l sis Society and ASTM Committee E-37 on Thermal Measurements. is the author or coauthor of 13 publications and 5 U.S. patents.
d
Marianne L. McKelvy is a Research Leader in the Spectrosco y Group
$the Analytical Sciences Laboratory, Dow Chemical, U.S.A., hidland, I. She received a B.S. degree fiom the Universz of Detroit (1979) and a M.S. degree (1982) and a Ph.D. (1985) $om the Polytechnic University,Brooklyn, Ny, Subsequently, she joined the Analytical Sciences Laboratory, where she zs znvolved zn solvzng polymer problems using infiared spectroscop Her research interests involve the characterization o polymers using vilrational spectrosco y and infiared microspectroscopy. Sfhe is a member of the Societyfor App&ed Spectroscopy and the Coblentz Society.
David M. Meunier is a Project Leader in the Plastics Group of the Analytical Sciences Laboratoty, Dow Chemical, U.S.A., Midland, MI. He received his B.S. in chemzstyfiom North Central Colle e in 1984 and his Ph.D. in analytical chemistry fiom the University ofIllinois in 1988. He joined Dow in that same year working in the Research Assignments Pro ram. His research interests involve the development and utilization ofsize exclusion chromatography, liquid chromatography, and combined techniques for characterizing complex polymer systems and polymer blends. Stephen W. Froelicher is a Research Leader in the Thermal Analysis
Group of the Analytical. Sciences Laboratory, Dow Chemical, U.S.A., Mzdland, MI, He receaved a B.S. de ree an chemzst (!980) fiom Northern Kentucky Universityand a P h . h in analytical cKemzstry (1985) from Purdue Unzverszty. He loaned Dow that same year and has been zn his current assignment since 1986. His research interests include the development and a plication of evolved gas analysis techniques such as thennogravimetryhass spectrometry for polymer characterazation. The emphasis of his research is understandtng the thermal and oxidative degradation of synthetic polymers under processing conditions.
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LIQUID CHROMATOGRAPHY
(Cl) Smith, C. G.; Smith, P. B.; Pasztor, A. J.; McKelvy, M. L.; Meunier, D. M.; Froelicher, S.W.; Ellaboudy, A S.Anal. Chem. 1 9 9 3 , 65,217R-243R (C2) Barth, H. G.; Boyes, B. E.; Jackson, C. Anal. Chem. 1 9 9 4 , fifi. - -, 59SR-620R. - - -. . . ---(C3) Revillon, A J. Li Chromatogr. 1 9 9 4 , 17, 2991-3023. (C4) Bruessau, R J. dakromol. Chem., Macromol. Symp. 1992,61, 199-218. (C5) Hagel, L. Chromatogr. 1993,648, 19-25. (C6 Hunt, B.f Anal. Proc. 1993,30, 338-340. (C7] Barth, H. G.; Regnier, F. E. Methods Carbohydr. Chem. 1 9 9 3 , 9, 105-114. (C8) GlBckner, G. Makromol. Chem., Macromol. Symp. 1992, 61, 239-243. (C9) Schunk, T. C. Chromatogr. A 1 9 9 3 , 656, 591-615. (C10) Provder, T., Ed! Chromato raphy of Polymers: Characterization b SEC and FFF; ACS symposium Series 521; American Zhemical Society: Washin on, DC, 1993. (C11) Smith, C. G., Buzanowsh, C., Graham, J. D., Iskandarani, Z., Eds. Handbook o Chromatography: Polymers; CRC Press: London, 1994; Vol. (C12) Garcia, R.; Porcar, I.; Campos, A.; Soria, V.; Figuemelo, J. E. J. Chromatogr. A 1 9 9 3 , 655, 191-198.
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