Photo-oxidative degradation of polyethylene: Effect of polymer characteristics on chemical changes and mechanical properties. Part 1—Quenched polyethylene

Photo-oxidative degradation of quenched samples of linear low density (LLD), medium density (MD) and two kinds of high density (HD) polyethylene (PE) films was studied using a medium-pressure mercury lamp. Greater amounts of crosslinking and build up of oxidation products were noticed in LLDPE than the other samples. The primary products of interaction between dienes and oxygen are considered to participate in the initiation of the photo-oxidation reactions. Using the FT-IR difference spectrum technique, the amount of branch concentration in the photo-irradiated PE samples was determined. Oxidation damage at the boundary region between crystalline and amorphous phases is considered to be important in determining the embrittlement time.     

Comparison of near-infrared and Raman spectroscopy for the determination of the density of polyethylene pellets

In this study, we compare near-infrared (NIR) and Raman spectroscopy for the determination of the density of linear low density polyethylene (PE) (in a pellet form). As generally known, Raman spectral features are more selective than those of NIR for most chemical samples. NIR spectroscopy has been more extensively used for the quantitative analysis of polymers, but Raman spectroscopy is the better choice as long as the problem of reproducibility of Raman measurements (especially for solid samples), mostly resulting from insufficient sample representation due to probing only localized chemical information and the sensitivity of sample placement with regard to the focal plane, can be overcome. To improve sample representation and reproducibility of Raman measurements, we have employed the wide area illumination (WAI) Raman scheme, capable of illuminating a laser onto a large sample area (28.3 mm²) for Raman spectral collection (a 6-mm laser spot with a focal length of 248 mm). Diffuse reflectance NIR spectra of PE pellets were collected using a sample moving system which allowed for the scanning of large areas. The prediction error was 0.0008 g cm⁻³ for Raman spectroscopy and 0.0011 g cm⁻³ for NIR spectroscopy. The harmonization of inherently selective Raman features and a reproducible spectral collection with correct sample representations using the WAI scheme led to an accurate determination of the density of the PE pellets.     

Improved accuracy for Raman spectroscopic determination of polyethylene property by optimization of measurement temperature and elucidation of its origin by multiple perturbation two-dimensional correlation spectroscopy

A novel strategy is demonstrated to improve the accuracy for determination of polyethylene (PE) density using Raman spectroscopy by optimizing the temperature of sample measurement. Spectral features associated with the conformation change of the polymer induced by temperature may provide valuable information to quantify important polymer properties such as density. To evaluate possible existence of an optimal temperature providing improved quantitative accuracy, Raman spectra of PE pellets with different densities were collected at eight different temperatures from 30 to 100 °C at 10 °C intervals. Using the spectral datasets collected at each temperature, partial least squares (PLS) models were developed using the reference PE density values determined by a standard density gradient method at 23 °C. Interestingly, the most accurate determination of density was realized at 70 °C. Multiple perturbation two-dimensional (MP2D) correlation analysis and differential scanning calorimetry (DSC) were used to examine the origin of improved accuracy at 70 °C. From these analyses, the pre-melt behavior of the PE samples was identified below their melting temperatures. Structural variations induced at the pre-melt stages enhance Raman spectral selectivity among the samples, thereby providing more accurate determination of PE density. The MP2D correlation analysis revealed the unforeseen thermal behavior of PE samples and successfully explained the improved accuracy at 70 °C.     

Rheo-optical near-infrared (NIR) spectroscopy study of low-density polyethylene (LDPE) in conjunction with projection two-dimensional (2D) correlation analysis

A rheo-optical characterization technique based on near-infrared (NIR) spectroscopy is developed specifically to probe the submolecular-level deformation caused during a mechanical test. An illustrative example of the mechanical deformation of low-density polyethylene (LDPE) is provided to show how it can be utilized. A set of NIR spectra of the polymer sample were collected by using an acousto-optic tunable filter (AOTF) NIR spectrometer coupled with a tensile testing machine as an excitation device. While the substantial level of variation of spectral intensity was readily captured during the mechanical deformation of the LDPE, main feature of the NIR spectra was overwhelmed by the contribution from the baseline change. Projection 2D correlation analysis was then applied to selectively extract the signal contribution from the baseline fluctuation. The 2D correlation spectra revealed the predominant extension of amorphous tie chains followed by the rotation of crystalline lamellae, which induce elastic and plastic deformation of the LDPE, respectively.     

Broad line NMR studies of linear and branched polyethylene

Temperature dependence of the shape and linewidth of the broad-line NMR spectra of commercially available high-density polyethylene (PE/HD), low-density polyethylene (PE/LD with ～3 per cent CH₃), block-copolythene (PE/AA with ～3 per cent acrylic acid) and polyethylene single crystal (PE/SC) were investigated to obtain information on the effect of branching and structural changes on the glass-transition temperature (Tg) and activation energy of molecular motion (E). The relatively lower value of Tg ～- ?100° for PE/HD compared to Tg ～- ?85° and ?60° for PE/CH₃ and PE/AA, along with the estimated lower value of E ～- 2·1 kcal/mole for PE/HD compared to 2·6 and 5·1 kcal/mole for PE/CH₃ and PE/AA, respectively, were interpreted by a molecular reorientational process connected mainly with the sidegroups of the main polymeric chains.     

Discrimination of ethylene/vinyl acetate copolymers with different composition and prediction of the content of vinyl acetate in the copolymers and their melting points by near-infrared spectroscopy and chemometrics

Near-infrared (NIR) diffuse reflectance spectra have been measured by use of a rotating drawer for pellets of 12 kinds of ethylene/vinyl acetate (EVA) copolymers with vinyl acetate (VA, the comonomer) varying in the 7–44 wt % range. They are unambiguously discriminated from one another by a score plot of the principal component analysis (PCA) Factor 1 and 2, based upon the NIR spectra pretreated by multiplicative scatter correction (MSC). Principal component (PC) weight loadings for Factor 1 show that the discrimination relies largely upon bands due to the overtone and combination modes arising from the VA unit. We have found one “outlier” in the score plot and elucidated its spectral characteristics based upon PC weight loadings for Factor 2. Partial least-squares (PLS) regression has been applied to propose calibration models which predict the VA content in EVA. The models have been prepared for three kinds of pretreatment, the first derivative, the second derivative, and MSC; and four kinds of wavelength regions. The NIR spectra in the 1100–2200 nm region after the MSC treatment has given the best correlation coefficient and standard error of prediction (SEP) of 0.998 and 0.70%, respectively. The calibration models, prepared by NIR diffuse reflectance spectroscopy for the pellet samples, are compared with previously reported models by NIR transmission spectroscopy for the flowing molten samples, and with those by Raman spectroscopy for the pellet samples. PLS regression has also allowed us to predict melting points of the copolymers with the correlation coefficient and SEP of 0.997 and 0.78°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1529–1537, 1998     

Two-dimensional infrared spectroscopy study on phase transition and structural variations of a hydrogen-bonded liquid crystal

Infrared (IR) spectra have been measured for a liquid crystal (LC) consisting of one trans-butene diacid (BD) molecule as a proton donor and two 4-(2,3,4-tridecyloxybenzoyloxy)-4'-stilbazoles (DBS) molecules as a proton acceptor (DBS:BD:DBS) linked together with each other by inter-molecular hydrogen bonds over a temperature range from 20 to 120 degrees C to explore its phase transition and heat-induced structural variations. The temperature-dependent IR spectra have shown that the inter-molecular hydrogen bonds are stable in the liquid crystalline phase but become slightly decoupled with temperature increasing. Two kinds of two-dimensional (2D) correlation spectroscopy, variable-variable (VV) and sample-sample (SS) 2D spectroscopy, have been employed to analyze the observed temperature-dependent spectral variations more efficiently. The SS 2D correlation analysis in the spectral range of 2700-1800 cm(-1) has demonstrated that a change in hydrogen bonds in the LC starts from 40 degrees C, which is not clarified by differential scanning calorimetry (DSC) and conventional IR and Raman spectroscopic analyses. On the other hand, the phase transition of LC revealed by SS 2D spectroscopy in the specific spectral regions of 1750-1650 and 3000-2700 cm(-1) is in a good agreement with that revealed by DSC for the heating process. The VV 2D correlation spectroscopy analysis has provided information about the structural variations of inter-molecular hydrogen bonds. The different species of hydrogen-bonded and free -COOH and -COO- groups in the LC have been clarified by the VV 2D correlation analysis. It has also elucidated the specific order of the temperature-induced structural changes in the intra- and inter-molecular hydrogen bonds concerning with the -COOH and/or -COO- groups in the LC.     

Application of two‐dimensional near‐infrared (2D‐NIR) correlation spectroscopy to the discrimination of three species of Dendrobium

The objective of this paper was to apply two‐dimensional (2D) near‐infrared (NIR) correlation spectroscopy to the discrimination of three species of Dendrobium. Generalized 2D‐NIR correlation spectroscopy was able to enhance spectral resolution, simplify the spectrum with overlapped bands and provide information about temperature‐induced spectral intensity variations that was hard to obtain from one‐dimensional NIR spectroscopy. The FT‐NIR spectra were measured over a temperature range of 30–140°C. The 2D synchronous and asynchronous spectra showed remarkable differences within the range of 5600–4750 cm⁻¹ between different species of Dendrobium. Copyright © 2009 John Wiley & Sons, Ltd.     

Pressure-induced variation of cellulose tablet studied by two-dimensional (2D) near-infrared (NIR) correlation spectroscopy in conjunction with projection pretreatment

Projection two-dimensional (2D) correlation analysis, achieved by selectively eliminating specific portion of dynamic spectra synchronized with the projecting vector, was used to study compression-induced variation of cellulose tablet monitored by near-infrared (NIR) spectroscopy and water sorption test. The increased density of the tablet by compression provided apparent variation of spectral intensity much larger than those caused by the change in the cellulosic structure. The direct calculation of 2D NIR correlation spectra from the raw spectra generated a relatively uninformative synchronous correlation spectrum and a very noisy asynchronous correlation spectrum due to the predominant intensity variation arising from the light scattering. In contrast, significant correlation features were elucidated without being hampered by the baseline fluctuation when the projection-corrected NIR spectra were constructed by the projection onto the space spanned orthogonal to the baseline change. Fine features of the compression-induced variation of the system were also elucidated by 2D hetero-correlation analysis based on the NIR spectra and water sorption profiles. The 2D correlation analysis revealed that the compression produces a disordered amorphous component of cellulose. The development of mobile amorphous phase results in a more tightly packed matrix with less porosity, which in turn prevents the penetration of water into the tablet and delays the water sorption.     

Application of two-dimensional near-infrared correlation spectroscopy to protein research

The purpose of the present paper is to demonstrate the potential of generalized two-dimensional (2D) near-infrared (NIR) correlation spectroscopy in studies of hydration and structure of proteins. We describe here two examples. The first example is concerned with heat denaturation process of ovalbumin in aqueous solutions and the second one deals with isomerizations with varying pH of serum albumin. New insight has been obtained into the hydration and unfolding process of secondary structures of ovalbumin and serum albumin by studying temperature- or pH-dependent correlation patterns in 2D synchronous and asynchronous spectra. Generalized 2D NIR correlation spectroscopy emphasizes spectral features not readily observable in conventional one-dimensional spectra, enabling to extract subtle but valuable structural changes concerning with the protein denaturation.     

Application of two-dimensional near-infrared correlation spectroscopy to the discrimination of Chinese herbal medicine of different geographic regions

Fructus Lycii is a traditional Chinese medicinal herb. The objective of this paper was to apply two-dimensional (2D) near-infrared (NIR) correlation spectroscopy to the discrimination of Fructus Lycii of four different geographic regions. Generalized 2D-NIR correlation spectroscopy was able to enhance spectral resolution, simplify the spectrum with overlapped bands, and provide information about temperature-induced spectral intensity variations that was hard to obtain from one-dimensional NIR spectroscopy. The 2D synchronous and asynchronous spectra showed remarkable differences within the range of 4950-5700cm(-1) between samples of different geographic regions. Using NIR instead of IR made the 2D approach more convenient and fast, and it can be applied to more area like process control. This approach can also be applied analogously to the discrimination of other Chinese herbal medicine of different geographic regions.     

中药口服固体制剂原辅料近红外光谱数据库的构建及应用

建立了中药口服固体制剂原辅料近红外(NIR)光谱数据库,采用模式识别方法研究了NIR光谱数据在物料分类和物性预测中的应用。使用便携式近红外光谱仪快速测量149批原辅料粉末的NIR漫反射光谱数据,并录入iTCM数据库。利用主成分分析(PCA)法探究NIR光谱数据对已知结构物料的分类能力,采用偏最小二乘(PLS)法研究了NIR光谱对原辅料物性参数和直接压片片剂性能的预测能力。经标准正态变量变换(SNV)+Savitzky-Golay(SG)平滑+一阶导数处理后的NIR光谱数据对微晶纤维素、乳糖、乙基纤维素、交联聚维酮和羟丙基甲基纤维素这5类辅料的区分能力较好。NIR光谱数据与原辅料粉末粒径、密度和吸湿性的相关性较强。NIR光谱信息作为物料物理性质的补充,可提高粉末直接压片片剂性能预测模型的性能。NIR光谱数据是iTCM数据库物性参数数据的补充,物性参数与NIR光谱数据的结合能更全面地表征原辅料的性质。     

FT-NIR Spectroscopy of some long-chain fatty acids and alcohols

Fourier-transform (FT) near-infrared (NIR) spectroscopy has proved to be a powerful technique in investigating structure and thermodynamic properties of long-chain fatty acids and alcohols. In order to extract useful information from the NIR spectra, bands due to the second as well as first overtones of OH-stretching modes of the monomeric forms were employed. It has been also found that two-dimensional (2D) NIR correlation spectroscopy can accentuate useful information often obscured in the complicated NIR spectral data set.     

The roles of carbohydrates, proteins and lipids in the process of aggregation of natural marine organic matter investigated by means of 2D correlation spectroscopy applied to infrared spectra

In this paper the marine organic matter soluble in an alkaline medium called extractable humic substance (EHS), was extracted from three sediment samples of Tyrrhenian Sea and separated by precipitation at pH 2 in the two fractions of fulvic acids (FAs) and humic acids (HAs). FAs were further fractionated in seven sub-samples of different molecular weight (mw) by means of seven different ultrafiltration membranes operating in the range between mw<1 kDa and mw>100 kDa. Then the qualitative composition of each sample of fractionated FAs and HAs was studied by means of one-dimensional Fourier transform infrared spectroscopy in reflectance mode (FTIR-DRIFT) and by two-dimensional (2D) correlation spectroscopy both in wavelength-wavelength (WW) and in sample-sample (SS) mode. The application of 2D correlation WW spectroscopy allows to elucidate the different roles played by carbohydrates and proteins with respect to some lipid compounds such as fatty acids and ester fatty acids during the process of aggregate formations from mw approximately 1 kDa to higher size aggregates. In addition, 2D correlation WW spectroscopy allows to observe some peculiar interactions between carbohydrates and proteins in the formation of EHS aggregates, interactions which vary from a sample to another sample. The results of 2D correlation SS spectroscopy confirm the general evidences obtained by 2D WW spectroscopy and moreover, they also describe the formation of EHS aggregates as a complex process where evolutionary links and connectivity between aggregates of neighbour molecular size ranges are not evident. Two-dimensional correlation spectroscopy applied to FTIR spectroscopy shows to be a powerful tool for the investigation of the mechanisms involved in EHS aggregation because it supports the acquisition of structural information which sometimes can be hardly obtained by one-dimensional FTIR spectroscopy.     

Application of Grey-correlated Spectral Region Selection in Analysis of Near-infrared Spectra

The optimal selection method of spectral region based on the grey correlation analysis was applied in the analysis of near-infrared(NIR) spectra. In order to compute “characteristic” spectral region, 160 samples of tobacco were surveyed by NIR. Next, the whole spectral region was randomly divided into six regions, and the values of association coefficients and correlation orders of different regions were computed for total sugar, reducing sugar and nicotine. Moreover, two regions that owned the largest value of association coefficient were regarded as “characteristic” spectral region of a model. Finally, the quantitative analysis models of different components were established via the partial least squares method, and the common selection methods of spectral region were compared. The simulation results indicate that the models to choose the spectral region based on grey correlation analysis are more effective than the common selection methods of spectral region, the optimized time of algorithm is shorter, the prediction precision of the models is higher and generalization ability for quantitative analysis results is stronger. This research can provide the support for the quantitative analysis models of NIR spectra and new idea for commercial analysis software of NIR. So, it has a high application value in the analysis of NIR spectra.     

Direct on-line Raman measurement of flying solid samples: determination of polyethylene pellet density

We demonstrated an on-line Raman measurement of polyethylene (PE) pellet density when it is flying in a sample line. While in flight, pellets are sparsely populated at spectral collection, a spectral collection strategy covering a large spatial volume (larger number of pellets simultaneously) is necessary to acquire reasonable Raman intensity. In addition, the Raman measurement must be less sensitive to pellet position, because position and distribution are uncontrollable in a flying condition. To fulfill these requirements, a wide area illumination (WAI) scheme capable of covering a large sample volume (illumination volume: 0.7 cm³) was used when the pellets were flying in a 2.5-cm-diameter sample line. In addition, a long focal length (250 mm) was used so that minor changes in pellet position would not significantly affect the resulting Raman spectral feature. Although Raman intensity substantially decreased due to the large void space among flying pellets, a correct spectral feature representing PE was successfully obtained without any significant spectral distortion. Using partial least squares (PLS) regression, the prediction error under flying conditions was 0.0009 g cm⁻³, which was comparable to that acquired when the pellets were packed (0.0008 g cm⁻³). When a conventional Raman scheme covering a smaller sample volume with a short focal length was used, the PE intensity decreased dramatically, and the resulting signal-to-noise ratio was not proper for quantitative analysis.     

Clarification of the thermally-induced pretransition of ribonuclease A in solution by principal component analysis and two-dimensional correlation infrared spectroscopy

Thermal denaturation of ribonuclease A (RNase A) in D₂O solution is studied by Fourier transform infrared (FT-IR) spectroscopy. Sample–sample two-dimensional correlation (SS 2D) spectroscopy and principal component analysis (PCA) are applied to these spectral data to reveal the thermal kinetics of RNase A. The second scores plot of PCA constructed from temperature-dependent original IR spectra illustrates a pretransition at 46 °C as well as a clear main transition at 66 °C. The latter is revealed by the SS 2D correlation spectra and the first score of PCA because of their illustration of the main denaturation event of RNase A, while the former cannot. Therefore, the present study demonstrates the great potential of PCA in revealing subtle phase transition of proteins in aqueous solutions.     

Two-dimensional near-infrared correlation spectroscopy studies of polymer blends I: Composition-dependent spectral variations of blends of atactic polystyrene and poly[2,6-dimethyl-1,4-phenylene ether]

Generalized two-dimensional (2D) near-infrared (NIR) correlation spectroscopy has been applied to study the conformational changes and molecular interactions in blends of atactic polystyrene (PS) and poly[2,6-dimethyl-1,4-phenylene ether] (PPE). NIR diffuse reflectance spectra have been measured for PS, PPE and their blends of different compositions, i.e., PS/PPE=90/10, 70/30, 50/50, 30/70, 10/90. The 2D synchronous correlation analysis of these composition-dependent NIR spectral variations separates the bands of PS from those of PPE. The 2D asynchronous analysis identifies spectral features indicative of the conformational changes or the specific interaction of PS and PPE. It can also detect “blend bands” whose origin is attributed to the formation of the polymer blends. Two “blend bands” of PS are identified at 6887 and 4836 cm⁻¹, and three “blend bands” of PPE are observed at 5752, 5679 and 4647 cm⁻¹. These “blend bands” are due to vibrations of the aromatic rings of PS or PPE and of the CH₃ of PPE. Thus, not only the aromatic rings of PS and PPE but also the CH3 groups of PPE play important roles in the formation of the blends.     

Prediction of some quality attributes of lamb meat using near-infrared hyperspectral imaging and multivariate analysis

The goal of this study was to explore the potential of near-infrared (NIR) hyperspectral imaging in combination with multivariate analysis for the prediction of some quality attributes of lamb meat. In this study, samples from three different muscles (semitendinosus (ST), semimembranosus (SM), longissimus dorsi (LD)) originated from Texel, Suffolk, Scottish Blackface and Charollais breeds were collected and used for image acquisition and quality measurements. Hyperspectral images were acquired using a pushbroom NIR hyperspectral imaging system in the spectral range of 900–1700 nm. A partial least-squares (PLS) regression, as a multivariate calibration method, was used to correlate the NIR reflectance spectra with quality values of the tested muscles. The models performed well for predicting pH, colour and drip loss with the coefficient of determination (R²) of 0.65, 0.91 and 0.77, respectively. Image processing algorithm was also developed to transfer the predictive model in every pixel to generate prediction maps that visualize the spatial distribution of quality parameter in the imaged lamb samples. In addition, textural analysis based on gray level co-occurrence matrix (GLCM) was also conducted to determine the correlation between textural features and drip loss. The results clearly indicated that NIR hyperspectral imaging technique has the potential as a fast and non-invasive method for predicting quality attributes of lamb meat.     

Fourier-transform infrared (FTIR) spectroscopy for monitoring and determining the degree of crystallisation of polyhydroxyalkanoates (PHAs)

FTIR spectroscopy has been used to monitor and determine the degree of crystallisation in a sample of polyhydroxybutyrate-co-14%valerate (PHB–co-14%HV). Time series spectra of solution-cast films of the polymer revealed spectral changes attributed to the onset of crystallisation. Curve fitting was used to obtain an absolute measure of crystallinity. Mean centred principal-component analysis (PCA) revealed that 99.9% of the spectral variance could be attributed to factor 1. The loadings plot for factor 1 contained features attributable to crystalline and amorphous phases. These features were opposite in sign, indicating that changes in the spectra with the onset of crystallisation are simultaneous and opposite in direction, i.e. as the crystalline band increases the amorphous band decreases. Cross-peaks in asynchronous 2D correlation maps indicate there are likely to be very minor components that are changing out of phase. The presence of these minor components is supported by examination of the loadings of higher factors in the PCA model. PCA has been shown to be suitable for determining the number of dynamic spectral features and has enabled relative and objective monitoring of crystallisation kinetics.