The use of near infrared (NIR) spectroscopy to study specific interactions in polymer blends

The purpose of this brief communication is to demonstrate how near infrared (NIR) spectroscopy can be used to study specific interactions is miscible polymer blends. We will first demonstrate, using model systems and blends of polycaprolactone (PCL) and phenoxy [poly(hydroxypropylether of bisphenol-A)], that information obtained from the OH stretch overtone absorption in the NIR is consistent with the information obtained from the OH stretch fundamental in the mid-IR region. We will then illustrate the advantages of NIR analysis of specific interaction with spectra obtained, over a range of temperatures, from thick (2 mm) films of blends of Nylon-6 and the zinc salt of sulfonated polystyrene (ZnSPS). © 1994 John Wiley & Sons, Inc.     

Light-scattering photometer with optical microscope for the in-line study of polymer extrusion

A light-scattering photometer with optical microscope for in-line studies during polymer processing is described. The instrument utilizes a commercial twin-screw extruding device that feeds molten polymer into a narrow slit die equipped with sapphire optical windows. The flow rate through the die is controlled via the feed rate, screw rate, and a by-pass valve. The optics for light scattering and microscopy can be switched back and forth via simple translation of a rail-mounted optical platform without realignment, allowing efficient in situ morphological studies in both real and reciprocal space. Extruded polystyrene/polyethylene blends and melts are used to demonstrate the performance and versatility of the instrument. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2935–2943, 1997     

The effect of different gloss levels on in-line monitoring of the thickness of printed layers by NIR spectroscopy

Near-infrared (NIR) reflection spectroscopy was used for monitoring the thickness or rather the coating weight of thin printed layers of transparent oil-based offset printing varnishes in a range from 0.5 to 5 g?m^?2. Quantitative analysis of the spectral data was carried out with partial least squares regression. Surface properties such as the gloss were found to strongly affect the prediction of the coating weight. This influence was minimized by the development of calibration models, which contained spectra of layers with a broad range of gloss levels. The prediction error of these models was in the order of 0.12 to 0.16 g?m^?2. In-line measurements were carried out at a sheet-fed offset printing press in order to test the performance of the models under real process control conditions. Varnishes were applied to paper at printing speeds of 90 or 180 m?min^?1. A close correlation between the predictions from in-line NIR spectra and the reference data from gravimetry was observed regardless of the specific degree of gloss of the layers (errors between 0.15 and 0.17 g?m^?2). The results clearly prove the efficiency of NIR reflection spectroscopy for quantitative investigations on thin layers in fast processes such as printing and demonstrate its analytical potential for quality and process control.

Petroleum resins adsorption onto quartz sand: near infrared (NIR) spectroscopy study

In this paper we have tried to evaluate adsorption parameters of petroleum resins. Near infrared (NIR) spectroscopy is applied for resins bulk concentration evaluation during adsorption process. NIR experimental scheme and parameters are provided. NIR spectra range of 9000-13,000 cm(-1) is chosen. Quartz sand (0.2-0.8 mm fraction) is used as adsorbent; benzene is used as solvent. Different approaches of "NIR spectra-resins concentration" calibration model building are discussed. Partial least squares (PLS) regression method is used. Langmuir model is chosen for experimental data fitting. Combined usage of kinetic and isothermic data gives us ability to evaluate the maximal adsorbed mass density, the equilibrium constant of adsorption, and the rate constants of adsorption (and desorption). The rate constants of resins adsorption and desorption are found to be concentration independent.     

近红外光谱法测定5-羟基色氨酸的含量

本文利用近红外光谱法建立了5-羟基色氨酸的偏最小二乘(PLS)定量模型。采用相关数法选择波段以及二阶导数、Norris derivative平滑滤波进行数据预处理,所建校正模型的R为0.99907,RMSEC为0.0638,RMSEP为0.0675。经验证模型的预测性能良好,为5-HTP的快速测定提供了一种方法。     

Building the quality into pellet manufacturing environment--feasibility study and validation of an in-line quantitative near infrared (NIR) method

The present study focuses on the implementation of an in-line quantitative near infrared (NIR) spectroscopic method for determining the active content of pharmaceutical pellets. The first aim was to non-invasively interface a dispersive NIR spectrometer with four realistic particle streams existing in the pellets manufacturing environment. Regardless of the particle stream characteristics investigated, NIR together with Principal Component Analysis (PCA) was able to classify the samples according to their active content. Further, one of these particle stream interfaces was non-invasively investigated with a FT-NIR spectrometer. A predictive model based on Partial Least Squares (PLS) regression was able to determine the active content of pharmaceutical pellets. The NIR method was finally validated with an external validation set for an API concentration range from 80 to 120% of the targeted active content. The prediction error of 0.9% (root mean standard error of prediction, RMSEP) was low, indicating the accuracy of the NIR method. The accuracy profile on the validation results, an innovative approach based on tolerance intervals, demonstrated the actual and future performance of the in-line NIR method. Accordingly, the present approach paves the way for real-time release-based quality system.     

The potential of mid infrared spectroscopy (MIRS) for real time bioprocess monitoring

The need for effective bioprocess (fermentation) monitoring is growing in importance due to the rapid pace of change in the fermentation industry, and attendant financial pressures. Vibrational spectroscopy has shown great promise in bioprocess monitoring. In particular, recently attention has been focused on the capability of mid infrared spectroscopy (MIRS) to monitor multiple analytes in highly complex fermentation fluids. The potential of this powerful analytical technique is critically evaluated by discussion of relevant studies. The advantages and limitations of MIR are discussed in the context of “rival” technologies, such as near infrared, focusing especially on employing such techniques in bioprocesses for real time (either in situ or ex situ) measurements. The potential barriers to the development of MIRS for real time monitoring are identified and further research directions highlighted.     

Near infrared reflectance spectroscopy (NIRS): A method of rational multicomponent analysis

With the introduction of chemometric evaluation software combined with diffuse reflectance measurements, near infrared spectroscopy has been launched into a new era of analytical applications. In the present contribution the basic principles of NIRS and its potential for chemical multicomponent analysis are discussed.     

Photoacoustic infrared spectroscopy of polymer beads

Photoacoustic (PA) spectra of four types of polymer resin beads, ranging in size from 35 to 150 μm, were acquired using a Fourier transform infrared spectrometer capable of both rapid- and step-scan mirror movement. Thermal diffusion lengths were on the order of the particle sizes of the beads. The PA magnitude spectra were similar to absorption spectra; both positive- and negative-going features occurred in the phase spectra. The frequency dependences of the total PA intensities of the polymer resins and carbon black differed by a factor of about f^−0.30. The intensities of the weak bands in the ratioed spectra (resin beads/carbon black) displayed a similar dependence. Partial saturation caused a more gradual variation for the stronger bands, where the intensity is proportional to f^−0.1–f^−0.2.     

胆酸含量的近红外分析数学模型

本文应用近红外技术研究了快速测定胆酸含量的方法.通过测定胆酸在10000~4000cm-1范围内的近红外透射光谱,基于偏最小二乘(PLS)算法,建立了胆酸含量的数学模型.以校正均方差(RMSEC)和相关系数(R)为指标,确定了用于建模的最优近红外波段和光谱预处理方法,并基于此模型预测了9个样品.结果显示,建模效果良好,...     

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.     

Near infrared reflectance spectroscopy for the fast identification of PVC-based films

Near infrared (NIR) reflectance spectroscopy was used to develop a non-destructive and rapid qualitative method for the analysis of plastic films used by the pharmaceutical industry for blistering. Three types of films were investigated: 250 microm PVC [poly(vinyl chloride)] films, 250 microm PVC films coated with 40 g m(-2) of PVDC [poly(vinylidene dichloride)] and 250 microm PVC films coated with 5 g m(-2) of TE (Thermoelast) and 90 g m(-2) of PVDC. Three analyses were carried out using different pre-treatment options and a PLS (partial least squares) algorithm. Each analysis was aimed at identifying one type of film and rejecting all types of false sample (different thickness, colour or layer). True and false samples from four plastics manufacturers were included in the calibration sets in order to obtain robust methods that were suitable regardless of the supplier. Specificity was demonstrated by testing validation sets against the methods. The tests showed 0% of type I (false negative identification) and 1% of type II errors (false positive identification) for the PVC method, 13 and 3%, respectively, for the PVC-PVDC method and no error for the PVC-TE-PVDC method. Type II errors, mostly due to the slight sensitivity of the methods to film thickness, are easily corrected by simple thickness measurements. This study demonstrates that NIR spectroscopy is an excellent tool for the identification of PVC-based films. The three methods can be used by the pharmaceutical industry or plastics manufacturers for the quality control of films used in blister packaging.     

Multiplexing fibre optic near infrared (NIR) spectroscopy as an emerging technology to monitor industrial bioprocesses

The application of near infrared spectroscopy in bioprocessing has been limited by its dependence on calibrations derived from single bioreactor at a given time. Here, we propose a multiplexed calibration technique which allows calibrations to be built from multiple bioreactors run in parallel. This gives the flexibility to monitor multiple vessels and facilitates calibration model transfer between bioreactors. Models have been developed for the two key analytes: glucose and lactate using Chinese hamster ovary (CHO) cell lines and using analyte specific information obtained from the feasibility studies. We observe slight model degradation for the multiplexed models in comparison to the conventional (single probe) models, decrease in r² values from 89.4% to 88% for glucose whereas for lactate from 92% to 91.8% and a simultaneous increase in the number of factors as the model incorporates the inter-probe variability, nevertheless the models were fit for purpose. The results of this particular application of implementing multiplexed-NIRS to monitor multiple bioreactor vessels are very encouraging, as successful models have been built on-line and validated externally, which proffers the prospect of reducing timelines in monitoring the vessels considerably, and in turn, providing improved control.     

Near infrared spectroscopy in the study of polymorphic transformations

The potential of near infrared (NIR) spectroscopy for the characterization of polymorphs in the active principle of a commercial formulation prior to and after the manufacturing process was assessed. Polymorphism in active principles is extremely significant to the pharmaceutical industry. Polymorphic changes during the production of commercial pharmaceutical formulations can alter some properties of the resulting end-products. Multivariate curve resolution-alternating least squares (MCR-ALS) methodology was used to obtain the “pure” NIR spectrum for the active principle without the need to pretreat samples. This methodology exposed the polymorphic transformation of Dexketoprofen Trometamol (DKP) in both laboratory and production samples obtained by wet granulation. No polymorphic transformation, however, was observed in samples obtained by direct compaction. These results were confirmed using by X-ray powder diffractometry (XRD) and differential scanning calorimetry (DSC) measurements. Pure crystalline polymorphs of DKP were available in the laboratory but amorphous form was not, nevertheless the developed methodology allows the identification of amorphous and crystal forms in spite of the lack of pure DKP.     

Near infrared fourier transform Raman spectroscopy of human artery

We report the first near IR FT-Raman spectroscopy of normal diseased human artery. In normal human aorta, two bands at 1669 cm⁻¹ and 1452 cm⁻¹ dominate the spectrum and can be assigned to protein amide I and C-H in-plane bending vibrations, respectively. Weaker bands are also observed between 1250 and 1350 cm⁻¹. Non-calcified atherosclerotic lesions with a large amount of necrotic debris below the tissue surface show a relative increase in the intensity of the 1452 cm⁻¹ band. In atherosclerotic aortas which contain calcified deposits several hundred microns below the tissue surface, a strong 961 cm⁻¹ band is observed due to the symmetric stretch of phosphate groups in the calcified salts. The results show that this method provides the capability to probe biological substituents several hundred microns below the tissue surface.     

Near infrared spectroscopy of stearic acid adsorbed on montmorillonite

The adsorption of stearic acid on both sodium montmorillonites and calcium montmorillonites has been studied by near infrared spectroscopy complimented with infrared spectroscopy. Upon adsorption of stearic acid on Ca–Mt additional near infrared bands are observed at 8236 cm^?1 and is assigned to an interaction of stearic acid with the water of hydration. Upon adsorption of the stearic acid on Na–Mt, the NIR bands are now observed at 5671, 5778, 5848 and 5912 cm^?1 and are assigned to the overtone and combination bands of the CH fundamentals. Additional bands at 4177, 4250, 4324, 4337, 4689 and 4809 cm^?1 are attributed to CH combination bands resulting from the adsorption of the stearic acid. Stearic acid is used as a model molecule for adsorption studies. The application of near infrared spectroscopy to the study of this adsorption proved most useful.     

Process monitoring of polymers by in-line ATR-IR, NIR and Raman spectroscopy and ultrasonic measurements

The aim of the present work is to show that spectroscopic and ultrasonic methods are powerful in situ methods for monitoring polymerization processes and for the determination of the composition of polymer blends and additives during extrusion. Quantitative analysis carried out with chemometric methods can determine the composition of multicomponent polymer mixtures and predict real world samples in real-time during extrusion. Examples are the modification of hyperbranched poly(urea-urethane)s, the polymerization of MMA, the real-time determination of flame retardants in PA, and the determination of the composition of the blend PE/PS. To cite this article: D. Fischer et al., C. R. Chimie 9 (2006).     

Fiber-optic evanescent wave fourier transform infrared (FEW-FTIR) spectroscopy of polymer surfaces and living tissue

The new method of fiber-optic evanescent wave Fourier transform infrared (FEW-FTIR) spectroscopy has been applied to studies of polymer surfaces and the diagnostics of normal, precancerous and cancerous tissue. This technique using optical fibers and fiber-optic sensors operating in the attenuated total reflection (ATR) mode in the mid-infrared (IR) region of the spectrum (850 – 1850 cm⁻¹) has found recently application in the area of tissue diagnostics. The method is suitable for noninvasive and rapid (seconds) direct measurements of the spectra of normal and pathological tissues in vitro, ex vivo, and in vivo. The FEW-FTIR technique is an ideal diagnostic tool for different types of soft, porous, foam, and rough polymer surfaces. Inhomogeneous coatings and defects on polymer surfaces as well as layer structures have also been detected by this method. It is convenient to apply this method to analyze large pieces of soft plastics and/or surfaces covered by plastics, since these types of surfaces are comparatively hard to analyze by traditional absorption spectroscopy. The FEW-FTIR technique is non-destructive, fast (15 seconds), and remote (up to a fiber length of 3m). In addition, it is sensitive enough to detect any changes in the vibrational spectra of a polymer surface, without heating and damaging it. The surfaces of polyethylene crumpled bags and rumpled films have been investigated in the range of 2000 – 1000 cm⁻¹. The distinct spectra of these surfaces as well as spectra of polytetrafluoroethylene have been recorded. The spectra of white and colored foams and different plastics have also been studied. Weak but distinct spectra have been recorded for carbon fibers (black, narrow fibers with a diameter of about 10 μm). Using the FEW-FTIR technique, measurements can be taken without preparing the sample. High quality spectra have also been obtained for the bulk and surfaces of apple, banana, grapefruit, and other food products. The method is expected to be further developed for geological and microelectronic applications.     

Dynamic Fourier transform infrared spectroscopy in polymer research

The rapid-scanning capability of FTIR instrumentation has revitalized the field of vibrational spectroscopy in polymer research and will be discussed with reference to the study of polyurethane kinetics, the temperature dependence of hydrogen bonding in polyamide 6 and strain-induced crystallization in a polydimethylsiloxane elastomer.     

NIR spectroscopy of selected iron(II) and iron(III) sulphates

A problem exists when closely related minerals are found in paragenetic relationships. The identification of such minerals cannot be undertaken by normal techniques such as X-ray diffraction. Vibrational spectroscopic techniques may be applicable especially when microtechniques or fibre-optic techniques are used. NIR spectroscopy is one technique, which can be used for the identification of these paragenetically related minerals and has been applied to the study of selected iron(II) and iron(III) sulphates. The near-IR spectral regions may be conveniently divided into four regions: (a) the high wavenumber region>7500 cm(-1), (b) the high wavenumber region between 6400 and 7400 cm(-1) attributed to the first overtone of the fundamental hydroxyl stretching mode, (c) the 5500-6300 cm(-1) region attributed to water combination modes of the hydroxyl fundamentals of water, and (d) the 4000-5500 cm(-1) region attributed to the combination of the stretching and deformation modes of the iron(II) and iron(III) sulphates. The minerals containing iron(II) show a strong, broad band with splitting, around 11,000-8000 cm(-1) attributed to (5)T(2g)-->(5)E(g) transition. This shows the ferrous ion has distorted octahedral coordination in some of these sulphate minerals. For each of these regions, the minerals show distinctive spectra, which enable their identification and characterisation. NIR spectroscopy is a less used technique, which has great application for the study of minerals, particularly minerals that have hydrogen in the structure either as hydroxyl units or as water bonded to the cation as is the case for iron(II) and iron(III) sulphates. The study of minerals on planets is topical and NIR spectroscopy provides a rapid technique for the distinction and identification of iron(II) and iron(III) sulphates minerals.