Crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) studied by 2D IR correlation spectroscopy

Crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx)) (HHx=12 mol%) was studied by means of two-dimensional infrared (2D IR) correlation spectroscopy. Three types of crystallization; the gradual cooling from the melt, the isothermal crystallization of the supercooled melt, and the isothermal crystallization of the solution-cast film were investigated. The order of crystal growth steps taking place during the three different types of crystallization processes was analyzed in detail. It was revealed by the asynchronous 2D correlation spectra generated from the dynamic IR spectra in the CO stretching band region that the development of the highly ordered crystals occurs prior to that of the less ordered crystals for the gradual cooling crystallization. On the other hand, for the supercooled melt and solution-cast film crystallization, the formation of the less ordered crystals takes place before that of the highly ordered crystals. The transition from the amorphous phase to the less ordered crystals is a simultaneous process for all three types of crystallization.     

Rapid determination of total Trans fat content by attenuated total reflection infrared spectroscopy: An international collaborative study

Interest in trans fat labeling has prompted efforts to develop new, more efficient methods for rapidly and accurately determining trans fat content in foods. The lower limit of quantitation, 5% trans fat (as percent of total fat), of transmission infrared official methods, such as AOAC 994.14 and 965.34, for total isolated trans fatty acids is too high to be generally useful for the determination of low levels of trans fats in foods. A novel and rapid (5 min) attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic procedure was recently developed and applied to food products. This procedure was voted official method AOCS Cd 14d-99 by the American Oil Chemists' Society in 1999 after testing in a 12-laboratory international collaborative study. The results of this study are described in this paper. Analytical ATR-FTIR results exhibited high accuracy in the range investigated, 1–40% trans; results tended to have <2% high bias relative to the gravimetrically determined values. The precision of this internal reflection method was found to be superior to those of transmission infrared official methods. It is recommended that the applicability of the ATR-FTIR method be limited to trans levels of >1% (as percent of total fat).     

Non-isothermal crystallization process of polyoxymethylene studied by two-dimensional correlation infrared spectroscopy

Non-isothermal crystallization process of polyoxymethylene (POM) from the melts was studied by two-dimensional correlation infrared spectroscopy. A hybrid structure of FCC (1135 cm⁻¹) and ECC (904 cm⁻¹) during the crystallization from the molten state was found. Non-isothermal kinetics of POM crystallization was also investigated using DSC curves. A newly perturbation-correlation moving-window two-dimensional (PCMW2D) technique was used to explore the complex crystallization process. We determined three processes in crystallization. The first is the initial stage of the crystal nucleus growing or the formation of certain local ordered structures in the melts. It can be inferred the formation of the crystal nucleus of FCC is earlier than that of the ECC. The second is the maximum crystallization temperature of POM. The last is the further improvements of crystals (especially in ECC) and the crystallization of the cyclic POM of low molecular weight. However, this process of FCC is slower than ECC. The temperature-dependent IR spectra at reheating were also analyzed using PCMW2D.     

Crystallization and melting behavior of iPP studied by DSC

This article is a part of a study of model and bulk composites, based on isotactic polypropylene (i-PP) and glass (or carbon) fibers, produced from knitted textile preforms of hybrid yarns. First, we report the results on crystallization and fusion of textile-grade i-PP, used for the processing of hybrid yarns and the corresponding knitted fabrics. The kinetics of the crystallization process, in the dynamic and isothermal regime, was followed by DSC, and the results were analyzed by Avrami, Ozawa, and Harnisch-Muschik methods. Isothermal crystallization of i-PP was carried out at 388–400 K, and values for the Avrami exponent ranging from 1.93 to 4.39 were determined. The equilibrium melting temperature was determined by the Hoffman-Weeks method, and γ = 2.54 was found. Double melting peaks were observed both when the crystallization was performed at lower temperatures (isothermal regime) and at higher cooling rates (nonisothermal regime). A single melting peak appeared upon melting following isothermal crystallization at 400 K. The nonisothermal kinetics data showed that the peak crystallization temperature changes from 377 to 386 K as the cooling rate decreases from 20 to 3 K/min. Applying the Ozawa method, a value of the exponent n = 2.33 was determined, which is in agreement with the results for isothermal crystallization at 391–400 K. The Harnisch-Muschik approach was also applied to compare the results for n, and a similar trend in the results of isothermal and nonisothermal crystallization was found, due to the predominant homogeneous mechanism of nucleation at lower cooling rates (lower isothermal T_c) in spite of being heterogeneous at higher cooling rates (higher isothermal T_c). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 395–404, 1998     

Characterization by Fourier transform infrared spectroscopy of polyethylene adipate/cholesteryl palmitate blends

FT‐IR spectroscopy has been employed to study compatibility, melting, and crystallization of the polyethylene adipate (PEA)/cholesteryl palmitate (CP) blends. The changes in FT‐IR spectra were followed by controlled rate of heating and cooling. The bands corresponding to the crystalline structure have been assigned. The accuracy of the transition temperature determination has been improved by fitting the curve of the integral absorbance dependence on temperature with a Boltzmann function. From dependence of the transition temperatures on the composition of the blend, it has been established that for each mixing ratio a certain mass fraction of CP should be dissolved in the PEA matrix. The PEA/CP blends behave as a phase‐separated system with partial miscibility. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1156–1163, 2004     

Hydration mechanism on a poly(methacrylic acid) film studied by in situ attenuated total reflection infrared spectroscopy

A drastic structure change during a hydration process of a poly(methacrylic acid) (PMAA) film was observed by time-resolved in situ attenuated total reflection infrared (ATR-IR) spectroscopy. Inter- or intra-hydrogen-bonds via side-chain carboxyl groups are formed as cyclic dimers, side-on dimers and linear open chain oligomers including open dimers in a dried PMAA film. By contacting water, the side-chain hydrogen-bonds in PMAA are dissociated instantly, and then the subsequent carboxyl groups which have no hydrogen-bond newly hydrate with water molecules in a side-on form. Quantum chemical calculations (QCCs) using a model monomer of propionic acid (PA) also support the hydrogen-bonded and hydrated structures explored by the ATR-IR spectroscopy. It has been concluded from the present study that the dissociation of hydrogen-bonded and newly created hydrated structures via the carboxyl groups play an important role for the swelling of PMAA in water.     

Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm⁻¹. This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction.     

Study of microbial polyhydroxyalkanoates using two-dimensional Fourier-transform infrared correlation spectroscopy

The premelting behavior of bacterially synthesized polyester poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), abbreviated as P(HB-co-HHx), was investigated by two-dimensional Fourier-transform infrared (2D FTIR) correlation spectroscopy. The temperature-dependent dynamic spectra were measured over a temperature range of 25–300°C. We focused our study on the thermally induced intensity fluctuations of bands for CO (1700–1760 cm⁻¹), C H (2910–3010 cm⁻¹) and C O C groups (1220–1310 cm⁻¹) stretching vibrations. Changes of crystalline conformation due to the thermal perturbation could be detected by the intensity and location variations of those characteristic bands responding to the variations of dipole moments. 2D correlation analysis indicated that the appearance of fully amorphous component did not happen simultaneously with the disappearance of crystalline component, suggesting that there was an intermediate state between ordered crystalline and amorphous states in P(HB-co-HHx). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 934–940, 2001     

Determination of totaltrans fatty acids in foods: Comparison of capillary-column gas chromatography and single-bounce horizontal attenuated total reflection infrared spectroscopy

The totaltrans fatty acid content of 18 food products was determined, after acid hydrolysis, extraction and methylation of fatty acids, by gas chromatography with a polar 100% cyanopropylsiloxane capillary column and by single-bounce horizontal attenuated total reflection spectroscopy (SB-HATR). Thetrans fatty acid methyl esters (FAME) of 9-hexadecenoate (9t-16:1), 9-octadecenoate (9t-18:1), and 9,12-octadecadienoate (9t,12t-18:2) were identified by comparison of their retention times with those of known standards and quantitated. The isomersc,t- andt,c-18:2 were identified from their published retention times and included in the quantitation oftrans FAME. Neat 50-μL portions of the FAME that were used for gas-chromatographic analysis also were analyzed by SB-HATR. This technique requires neither weighing nor quantitative dilution of test portions prior to spectroscopic quantitation of isolated double bonds oftrans configuration. A symmetric 966-cm⁻¹ absorption band on a horizontal background was obtained from unhydrogenated soybean oil FAME as the reference material. For 9 of 11 products withtrans fat content>5% of total fat, results obtained by SB-HATR were higher than those obtained by gas chromatography. Results obtained by the gaschromatographic procedure were slightly to significantly higher than those obtained by SB-HATR for the six foods in whichtrans fat content was <5% of total fat.     

Acid properties of mazzite zeolites studied by IR spectroscopy

The adsorption of ammonia, pyridine and benzene on non-dealuminated (Si/Al = 4.4) and dealuminated (Si/Al = 10 and 30) mazzite samples was followed by FT-IR spectroscopy. The dealumination of mazzites (by steaming and acid treatment) made all their narrow channels accessible to pyridine. Pyridine and ammonia adsorption and desorption showed that the broad OH band at approximately 3600 cm⁻¹ was composed of several submaxima corresponding to hydroxyl groups of various localizations and various acid strengths. With all the mazzite samples, the concentrations of Brönsted acid sites determined by ammonia adsorption were comparable with the values calculated from the chemical composition of zeolites (amounts of Al minus amount of Na) whereas those determined from pyridine adsorption were lower than these values. The greatest difference was found for the non-dealuminated MAZ-4.4, in which pyridine could not reach the sites of the narrow channels. The values of the extinction coefficients corresponding to the OH groups located in the large channels were higher than those corresponding to the OH groups of the narrow channels, thus showing the stronger acidity of the former OH groups. The acid strength of OH groups increased with the dealumination, as seen from the increase in the corresponding extinction coefficient and frequency shift Δν due to the hydrogen bonding of hydroxyl groups with benzene. Furthermore, the protonic acidity of the dealuminated mazzite of Si/Al = 30 was found to be stronger than that of mordenite and beta zeolite with comparable Si/Al.     

Multiple melting behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) investigated by differential scanning calorimetry and infrared spectroscopy

The multiple melting behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx)) (HHx = 12 mol%) isothermally crystallized from the melt state has been characterized by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The influence of different experimental variables (such as crystallization temperature, time, and heating rate) on the multiple melting behavior of P(HB-co-HHx) was investigated by using DSC. Moreover, it has been further examined by monitoring intensity changes of the characteristic IR bands during the subsequent heating process. For the isothermally crystallized P(HB-co-HHx) samples, triple melting peaks were observed upon heating. The weak lowest-temperature DSC endotherm I always appears at the position just above the crystallization temperature, and shifts to a higher temperature linearly with the logarithm of the crystallization time. The combination of DSC and IR results suggested that the occurrence of peak I was a result of the melting of crystals formed upon long-time annealing. As for the other two main melting endothermic peaks, endotherm II corresponds to the melting of crystals formed during the primary crystallization, and endotherm III is ascribed to the melting peak of the crystals formed by recrystallization during the heating process.     

A two dimensional infrared correlation spectroscopic study on the structure changes of PVDF during the melting process

Two-dimensional infrared (2D IR) correlation spectroscopy was applied to study the conformation change during poly(vinylidene fluoride) (PVDF) melting process. The absorption spectral changes are observed with increasing temperature. These observed changes in IR spectra might be attributed to three kinds of PVDF components: α-PVDF, β-PVDF, and amorphous component. 2D IR correlation analysis indicates that during melting process three kinds of PVDF component change asynchronously: above all, the amorphous component relaxes its molecule chains, and then the β-PVDF transfers to amorphous component, finally the α-PVDF transfers to amorphous component.     

Comparison of attenuated total reflection infrared spectroscopy to capillary gas chromatography for trans fatty acid determination

Gas chromatography (GC) has been a standard analytical tool in lipid chemistry. The rapid attenuated total reflection (ATR) infrared (IR) American Oil Chemists’ Society (AOCS) Recommended Practice (Cd 14d-97) was compared to the capillary GC AOCS Recommended Practice (Ce 1f-97) that was optimized to accurately determine total trans fatty acids on highly polar stationary phases. This comparative evaluation was validated in an independent laboratory. These procedures were used to quantitate the total trans fatty acid levels in partially hydrogenated vegetable oils, measured as neat (without solvent) triacylglycerols (TAG) by ATR and as fatty acid methyl ester (FAME) derivatives by capillary GC. Unlike FAME, TAG determination by ATR required no derivatization, but samples had to be melted prior to measurement. Five blind replicates for each of three accuracy standards and three test samples were analyzed by each technique. The GC and ATR determinations were in good agreement. Accuracy was generally high. The ratios of ATR mean trans values (reported as percentage of total TAG) to the true values (based on the amount of trielaidin added gravimetrically) were 0.89, 0.98, and 1.02 for accuracy standards having about 1, 10, and 40% trans levels. The corresponding GC values, determined as percentage of total FAME, were 0.98, 0.99 and 1.04. The ratios of mean trans values determined by these techniques were ATR/GC 0.85, 1.04, and 1.01 for test samples having trans levels of about 0.7, 8, and 38%, respectively. The optimized GC procedure also minimzed the expected low bias in trans values due to GC peak overlap found with the GC Official Method Ce 1c-89. Satisfactory repeatability and reproducibility were obtained by both ATR and GC.     

Characterization of edible oils,butters and margarines by Fourier transform infrared spectroscopy with attenuated total reflectance

The combination of attenuated total reflectance (ATR) and mid-infrared spectroscopy (MIRS) with statistical multidimensional techniques made it possible to extract relevant information from MIR spectra of lipid-rich food products. Wavenumber assignments for typical functional groups in fatty acids were made for standard fatty acids: Absorption bands around 1745 cm⁻¹, 2853 cm⁻¹, 2954 cm⁻¹, 3005 cm⁻¹, 966 cm⁻¹, 3450 cm⁻¹ and 1640 cm⁻¹ are due to absorption of the carbonyl group, C−H stretch, =CH double bonds of lipids and O−H of lipids, respectively. In lipid-rich food products, some bands are modified. Water strongly absorbs in the region of 3600–3000 cm⁻¹ and at 1650 cm⁻¹ in butters and margarines, allowing one to rapidly differentiate the foods as function of their water content. Principal component analysis was used to emphasize the differences between spectra and to rapidly classify 27 commercial samples of oils, butters and margarines. As the MIR spectra contain information about carbonyl groups and double bonds, the foods were classified with ATR-MIR, in agreement with their degree of esterification and their degree of unsaturation as determined from gas-liquid chromatography analysis. However, it was difficult to differentiate the studied food products in terms of their average chainlength.     

Isothermal crystallization behavior and melting characteristics of injection sample of nucleated polypropylene

The isothermal crystallization behavior and melting characteristics of pure polypropylene (PP) and PPs nucleated with a phosphate nucleating agent (A) and a sorbitol derivative (D) have been studied by differential scanning calorimetry (DSC). Compared with pure PP, nucleated PPs show a shorter half‐times of crystallization. Dependence of crystallization rate of nucleated PP on the crystallization temperature is stronger than that of pure PP at the higher crystallization temperature, whereas the opposite results are obtained at the lower crystallization temperature. Addition of nucleating agent shifts the temperature at the deviation from the baseline of DSC melting curve, T, and the temperature at the completion of melting, T, to higher temperatures, indicating that nucleated PPs exhibit a higher perfection of PP crystals. A shoulder peak in the high temperature range of melting peak of nucleated PP and a wider low temperature region in the melting peak of pure PP are observed. Obviously, PP and nucleated PPs form different distribution of crystal perfection in the isothermal crystallization process. According to the half‐time of crystallization, nucleating agent A is more effective than D. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2547–2553, 2000     

iPB/PP合金的相容性、熔融及结晶行为

采用双螺杆挤出机熔融挤出制备高全同聚1-丁烯(iPB)/聚丙烯(PP)合金,采用动态热机械分析仪和差示扫描量热仪研究其相容性及熔融结晶行为。结果表明:iPB/PP为部分相容体系;iPB和PP的熔融温度、熔融焓均随对方组分含量的增加而逐渐降低,两者相互干扰了对方结晶的完善程度和结晶度;当m(iPB)/m(PP)=60∶40时,iPB结晶温度提高2.8℃,PP结晶温度提高3.8℃,两者相互影响、促进了对方的结晶;w(PP)为10%~70%时,iPB的结晶速率提高显著。     

Surface crystallization of poly(ethylene terephtalate) studied by atomic force microscopy

Poly(ethylene terephtalate) (PET) crystallization was shown by atomic force microscopy (AFM) to occur at 85 °C in the first few nanometers near the polymer-air interface. The surface was fully transformed into spherulites after 30 min, while no signs of bulk crystallization were observed by FTIR. All the observed spherulites presented a nucleation centre, indicating that the crystallization process started at the surface of the film. Tapping mode AFM confirmed that the spherulites were not covered by an amorphous layer. The most probable explanation is a decrease of T_g near the surface. Due to the poor crystallization conditions, the constitutive units of the spherulites were small crystalline blocks. By changing the annealing time, it was possible to produce PET surfaces with different surface fractions consisting of semi-crystalline material (spherulites) and amorphous matrix. This provided a controlled surface heterogeneity on the submicrometer scale, with a contrast in terms of stiffness, roughness and swelling by organic solvents.     

The interaction of butenes with Cu ions in CuMCM-41 studied by IR spectroscopy

As CuMCM-41 was found to be active in skeletal isomerisation of n-butenes, we followed by IR spectroscopy the interaction of but-1-ene, cis-but-2-ene, and trans-but-2-ene with Cu⁺ sites in CuMCM-41. It has been revealed that Cu⁺ activated strongly CC bond, what resulted in a frequency shift of CC stretching band by about 100 cm⁻¹. Moreover, the vibration of CH bonds in CH₂ and CH groups neighbouring to the double bonds was also perturbed. We suppose that the activation of CC bond is a result of π-back donation of d electrons of Cu⁺ to π^* antibonding orbitals of butenes. IR results evidenced also the heterogeneity of Cu⁺ sites in CuMCM-41 and the presence of Cu⁺ sites of various electron donor properties. But-1-ene molecules bonded to Cu⁺ ions are less prone to accept protons from Brønsted acid sites than molecules bonded by hydrogen bonding to non-acidic SiOH groups, even though they are more negative than free or physisorbed molecules. The IR studies of coadsorption of CO and but-1-ene suggest that the interaction of CO with Cu⁺ is much weaker if but-1-ene is present, than without butene.     

Determination of trans fatty acids in hydrogenated vegetable oils by attenuated total reflection infrared spectroscopy: Two limited collaborative studies

An attenuated total reflection infrared spectroscopy procedure was collaboratively studied among two sets of five laboratories for quantitating the total trans fatty acid levels in neat (without solvent) hydrogenated vegetable oils, measured as triacylglycerols in one study, and as fatty acid methyl ester derivatives in the other. Unlike the fatty acid methyl esters, the triacylglycerols required no derivatization but had to be melted prior to measurement. To obtain a symmetric absorption band at 966 cm⁻¹ on a horizontal background, the single-beam spectrum of the trans-containing fat was "ratioed" against that of a refined oil or a reference material that contained only cis double bonds. A single-bounce horizontal attenuated total reflection cell that requires 50 μL of undiluted test samples was used for oils, melted fats, or their methyl esters. For fatty acid methyl esters, the reproducibility relative standard deviations were in the range of 0.9 to 18.46% for 39.08 to 3.41% trans, determined as methyl elaidate per total fatty acid methyl esters. For five pairs of triacylglycerol blind duplicates, the reproducibility and repeatability relative standard deviations were in the ranges of 1.62 to 18.97%, and 1.52 to 13.26%, respectively, for 39.12 to 1.95% trans, determined as trielaidin per total triacylglycerols. Six pairs of spiked triacylglycerol blind duplicates (quality assurance standards) exhibited high accuracy in the range of 0.53 to 40.69% trans and averaged a low bias of 1.3%. These statistical analysis results were compared to those collaboratively obtained by the recently adopted AOCS Cd14-95 and AOAC 994.34 Infrared Official Methods.     

Study of melting and crystallization behavior of polyacrylonitrile using ultrafast differential scanning calorimetry

The thermal behavior of polyacrylonitrile (PAN) has been investigated using X-ray diffraction, differential scanning calorimetry (DSC), and ultrafast DSC. In conventional DSC, it is difficult to prevent the concurrent occurrence of the exothermic reactions of PAN with melting. However, in the ultrafast DSC curve, the exothermic peak due to these reactions disappears over the temperature range 0–400 °C at heating rates above 250 °C s⁻¹. Alternatively, the glass transition and the melting of PAN are observed over the temperature range 109–129 °C and 335–362 °C, respectively. Moreover, upon cooling from the molten state at a rate of −7500 °C s⁻¹, PAN crystallization is observed at 204 °C. These findings were observed repeatedly during heating and cooling measurements. From the extrapolation analysis, the zero-entropy-production melting temperature of PAN is found to lie in the temperature range 320–350 °C. Finally, the equilibrium melting temperature of PAN is estimated to be ca. 465 °C.