On‐line NIR sensing of CO2 concentration for polymer extrusion foaming processes

An on‐line sensor using near infrared (NIR) spectroscopy is developed for monitoring CO₂ concentration in polymeric extrusion foaming processes. NIR absorption spectra are acquired by a probe installed at the foaming extruder die. The calibration curve relating the absorbance spectrum at 2019 nm to the dissolved gas concentration is derived so as to infer dissolved CO₂ gas concentration on‐line from measured NIR spectra. Experimental results show the developed on‐line NIR sensor can successfully estimate dissolved CO₂ concentration in the molten polymer and illustrate that the developed NIR sensing technique is among the more promising methods for quality control of polymeric extrusion foaming processes.     

Visualization of hydrolysis in polylactide using near‐infrared hyperspectral imaging and chemometrics

The hydrolysis of polylactide (PLA) occurs during melt processing, leading to product defects in, for example, appearance and mechanical properties. Hydrolyzed PLA products, whose mechanical properties were deteriorated, must be detected during processing to ensure the quality control of PLA products. In this study, near‐infrared (NIR) hyperspectral imaging was applied for evaluating the extent of hydrolysis. NIR spectra in the wavelength range from 1200 to 1600 nm were changed by (1) hydrolysis induced by molding and (2) crystallization induced by annealing. The changes in the NIR spectra mediated by these two factors were distinctly different but overlapping, leading to difficulty in evaluating PLA at only a single wavelength. Partial least squares regression was introduced for detecting the hydrolyzed PLA. NIR imaging combined with the constructed partial least square models clearly visualized the differences in the extent of hydrolysis in hydrolyzed PLA under varying degrees of crystallization. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45898.     

Monitoring and control of styrene solution polymerization using NIR spectroscopy

Tailored polymer resins are frequently required for a given application. The lack of instruments for in‐line monitoring of polymer quality has long been recognized as an important problem in polymerization reactor control. Using the styrene solution polymerization system as an example, we present the use of near‐infrared (NIR) spectroscopy as an alternative tool for in‐line and in situ monitoring and control of monomer conversion and average molecular weight of polymer resins. By using a Kalman filter state estimator and an accurate first‐principle model, the control loop could be successfully closed to track desired monomer values and average molecular weights. Two process control strategies, one based on the optimal control theory and the other on model predictive control, were implemented both theoretically and experimentally. The experimental results showed that it is feasible to use NIR spectroscopy for the simultaneous control of monomer conversion and polymer average molecular weight. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1273–1289, 2003     

FT–NIR as a determination method for reinforcement of polymer nanocomposites

Layered silicates as nanoscale fillers have a great potential in improving polymer material properties. Depending on the composite structure (agglomerated, intercalated, or exfoliated) a significantly higher level of reinforcement of the virgin polymer can be achieved with a very small amount of filler. The morphology of the composites is usually characterized by XRD and microscopic methods (e.g., transmission electron microscopy). But the level of reinforcement of nanocomposites is not always proportional to morphology (delamination level of the silicate layers). A new approach for characterizing the material reinforcement level as a consequence of melt quality is to correlate the results of extensional rheometry (level of melt strength) with those of near infrared (NIR) spectroscopy. The advantage of the NIR technique is the suitability for in‐line implementation by using quartz based optics and optical fibers for the signal transfer from the measuring probe to the NIR spectrometer. The presented results show a direct correlation between the reinforcement level determined by rheotens measurements and the data analyzed from off‐line NIR measurements. The results of the chemometric analysis of the NIR data shows that this in‐line capable optical method provides quantitative information on the quality of the nanocomposite. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Determination of Mechanical and Optical Properties of Eucalyptus Kraft Pulp by NIR Spectrometry and Multivariate Calibration

Abstract

Multivariate data analysis and NIR spectrometry were used to determine the mechanical and optical properties of eucalyptus kraft pulps with different chemical compositions and refined to different levels. Tear (TrID), tensile (TsID), burst (BuID), and bending (BeID) indexes and elastic modulus (EM), stretch (ST), and breaking length (BL) were the mechanical properties measured. Measurement of beating degree (SR) was also achieved. Light scattering (LS) and light absorption (LA) coefficients were the optical properties measured. Mechanical and optical properties were modeled using NIR spectra obtained on pulp hand sheets by diffuse reflectance and application of the partial least squares (PLS) method. Models with two to seven PLS components and very good predictive ability were established after testing the first‐derivative, Kubelka‐Munk, or a combination of both as pre‐processing techniques. Models were validated by using cross‐validation methodology and a comparison of measurements using conventional methods for new samples. The predictive models can reduce time in traditional measurements in the pulp and paper industry and are suitable for direct application using “at‐line” conditions. As an additional benefit, improvements in process monitoring and paper quality can be achieved.     

In‐line near‐infrared spectroscopy: A tool to monitor the preparation of polymer‐clay nanocomposites in extruders

In‐line diffuse reflectance and on‐line transmission near‐infrared spectroscopy (NIR) measurements are performed at the same location of the barrel of a twin screw extruder during the preparation of a polypropylene/clay nanocomposite. Their performance is evaluated by means of a 7‐parameter chemometric model using off‐line rheological and structural (FTIR) data obtained from samples prepared under different screw speed, compatibilizer content and clay loading, as well as a process‐related thermomechanical index. Despite the higher variability of the diffuse reflectance signal, the two models present analogous high quality indices. The aptness of the reflectance measurements is thus validated, which has direct practical advantages, as this probe can be fixed in any typical melt pressure transducer port. The probe is then used for the real‐time in‐line monitoring of the production of the same nanocomposite but now using different throughputs, and the chemometric‐based predictions are compared with experimental off‐line characterization data. The nonlinear effect of throughput is correctly anticipated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Near‐Infrared Broadband Photoluminescence of Bismuth‐Doped Zeolite‐Derived Silica Glass Prepared by SPS

Through the order–disorder transition process of zeolites, bismuth‐doped zeolite‐derived silica glasses with broadband near‐infrared (NIR) photoluminescence have been successfully prepared by spark plasma sintering (SPS). The samples were characterized by X‐ray diffraction, UV‐vis, photoluminescence, and fluorescence lifetime. The results showed that as‐prepared samples possessed favorable broadband NIR luminescence. The NIR emission (peaked at ~1140 nm) intensity decreased with increasing the bismuth doping concentration when excited by 500 and 700 nm. The tendency was different from the emissions (peaked at ~1240 nm) excited by 800 nm. In addition, the NIR fluorescence peaks of the fixed Bi concentration sample can be observed almost around 1140 or 1240 nm when excited by different wavelengths from 500 to 950 nm. These phenomena implied that the NIR emission peaked at different wavelengths may originate from different bismuth species. Three kinds of Bi active centers Bi⁺, Bi⁰, and (Bi₂)^2? were proposed to contribute to the NIR emission peaks at ~1140, 1240, and 1440 nm, respectively. Interestingly, a broadband NIR emission peaked at 1207 nm with a full‐width at half maximum of 273 nm was observed when excited by 600 nm, whose intensity was stronger than that excited by 800 nm. This property might be useful for broadband fiber amplifiers and tunable lasers.     

Preparation and characterization of poly(styrene butylacrylate) latex/nano‐ZnO nanocomposites

Poly(styrene butylacrylate) latex/nano‐ZnO composites were prepared by blending poly(styrene butylacrylate) latex with a water slurry of nano‐ZnO particles, and the effects of certain parameters, such as particle size, dispersant type, dispersing time and others, on the dispersibility, mechanical properties, ultraviolet (UV) shielding and near infrared (NIR) shielding were investigated with transmission electron microscopy (TEM), an Instron testing machine, dynamic mechanical analysis and ultraviolet‐visible‐near infrared (UV‐VIS‐NIR) spectrophotometry. TEM observation showed that dispersants with long chains are better than those with short chains at enhancing the dispersibility of nano‐ZnO particles in a matrix; extending dispersing time also improves the dispersibility of nano‐ZnO particles in a matrix. Instron tests showed that the nanocomposite polymers embedded with nano‐ZnO particles had much higher tensile strength than the corresponding composite polymers with micro‐ZnO particles. As the nano‐ZnO content increased, the temperature of glass transition (T_g) of the nanocomposite polymer embedded with 60 nm ZnO particles first increased then decreased, but 100 nm ZnO and micro‐ZnO particles seemed to have no influence on the T_g of the composite polymers. The better dispersibility of nano‐ZnO particles resulted in higher T_g values. Increasing nano‐ZnO content or dispersibility could enhance the UV shielding properties of the nanocomposite polymers, and 60 nm ZnO particles could more effectively shield UV rays than 100 nm ZnO particles. Micro‐ZnO particles basically had no effect on the UV absorbance of the composite polymers. A blue‐shift phenomenon was observed at 365 nm when nano‐ZnO particles were present in the nanocomposite polymers. NIR analysis indicated that as nano‐ZnO content increased, the NIR shielding of the nanocomposite polymers increased, but the NIR shielding properties seemed to be more influenced by particle size than by the nano‐effect. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1923–1931, 2003     

Preparation and characterization of UV‐curable organic/inorganic hybrid composites for NIR cutoff and antistatic coatings

In this study, UV‐curable organic/inorganic hybrid composite coatings with near infrared (NIR) cutoff and antistatic properties were prepared by high‐shear mixing of two kinds of polymer matrices and coated on plastic and glass substrates by the doctor‐blade method. This study also investigated the morphology, stability, optical properties, electrical resistivity, and durability of the UV‐cured composite coats. It was found that the composite coatings were very stable under centrifugation. Moreover, the films with transmittance of above 80% in a visible light region (400–800 nm) and of ～ 40% to 50% in the NIR region (1000–1600 nm) showed low haze of 6.9%, electrical resistivity of around 2.3 × 10⁷ Ω/square. Thus, excellent adhesion, scratch, and weathering durability can be produced on polycarbonate substrate at room temperature. The experimental results reveal that UV‐curable organic/inorganic hybrid composites can be used effectively to fabricate films with NIR cutoff as well as antistatic properties, indicating a high potential for practical application in architectural, automotives, and optoelectronics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

NIR,DSC, and FTIR as quantitative methods for compositional analysis of blends of polymers obtained from recycled mixed plastic waste

Methods for the determination of the composition of two binary blends in mixtures of recycled polymeric materials were analyzed and compared. Recycled polypropylene/polyethylene (PP/HDPE) and recycled poly(acryl‐butadiene‐styrene) and polypropylene(ABS/PP) were used to develop and validate the methods. Diffuse reflectance near infrared spectroscopy (NIRS) offers high sensitivity and ease of operation and a possibility to perform multivariate data analysis. In comparison, differential scanning calorimetry (DSC) and Mid‐IR, which are commonly used for this purpose require certain sample preparation and are indeed time consuming. In addition, the low sensitivity of these two methods to concentrations lower than 1% wt makes their application in quality control of recycled polymers inappropriate. NIR can be used for estimating the composition of the recyclate on‐line in only a few seconds, no sample preparation is required, and high precision is achieved. We obtained a root mean square error of prediction (RMSEP) equal to 0.21% wt in the interval from 0‐15% wt of PP in HDPE and a RMSEP equal to 0.91% wt in the interval 0‐100%. For blends of PP/ABS a RMSEP of 0.74% wt in the range 0‐100% and 0.32% wt in the range 0‐15% wt PP was calculated. Most of the variation in the spectral data with respect to the polymer blend composition for all the studied blends were explained by two principal components (PC). The optimal number of factors (PC) was determined by cross‐validation analysis.     

La2O2SO4:RE/Yb new phosphors for near infrared to visible and near infrared upconversion luminescence (RE=Ho,Er, Tm)

The 3 new upconversion (UC) phosphors of La₂O₂SO₄:RE/Yb (RE=Ho, Er, and Tm, respectively) were derived via facile dehydration of their layered hydroxide precursors that were hydrothermally synthesized at 100°C. Rietveld XRD refinement found contracting cell dimension with decreasing RE³⁺ size, confirming the direct crystallization of solid solution. The Er³⁺ and Ho³⁺ activators both exhibited simultaneous green and red (dominant) emissions under 978‐nm near‐infrared (NIR) laser excitation (NIR‐Vis UC). Particularly, Tm³⁺ produced a Gaussian‐shaped pure NIR emission band at ~812 nm via its ³H₄ → ³H₆ transition (NIR‐NIR UC), which is highly desired for NIR biological application. Analysis of the excitation‐power dependent UC properties manifested a 3‐photon mechanism for the 3 phosphors, and the possible photon reactions leading to UC were illustrated.     

Preparation of poly(vinyl alcohol) films with promising physical properties in comparison with commercial polyethylene film

Poly(vinyl alcohol) (PVA) films with different thicknesses (0.08, 0.2, 0.23, 0.42 mm) were prepared by a casting technique. The transmission and the absorption of the PVA films were measured as functions of the wavelengths. PVA film with a thickness of 0.42 mm showed zero transmission in the wavelength range of 190–350 nm. The transmission spectrum of a commercial polyethylene film with a thickness of 0.21 mm was compared to the transmission spectrum of PVA film with a thickness of 0.42 mm. A correlation was found between the two transmission spectra in the region 190–350 nm and a 20% increase in the transmission of the PVA film in comparison with the transmission of commercial polyethylene in the region 350–1500 nm. The near‐infrared region of the transmission of commercial polyethylene was increased by 15% with respect to the transmission of the PVA film. The stress–strain measurements were done for PVA and commercial polyethylene films. The Young's modulus and the strength at break for PVA films are higher by two orders of magnitude than those for commercial polyethylene film. The strain at break for commercial polyethylene is 17% lower than that for PVA film. Radiation effects on the optical properties of PVA and commercial polyethylene films were investigated. The PVA and commercial polyethylene films were irradiated with a xeon arc lamp at 3.5–5 W/cm². The optical properties for PVA and commercial polyethylene films were studied after irradiation. The obtained results showed that PVA film with a thickness of 0.42 mm gave promising properties which could be used in technological applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1219–1226, 2002     

Simultaneous determination of molecular weight and crystallinity of recycled HDPE by infrared spectroscopy and multivariate calibration

An attempt of correlating molecular weight (M_n) of recycled high‐density polyethylene (HDPE) as measured by size‐exclusion chromatography (SEC) with diffuse reflectance near and mid‐infrared spectroscopy (NIR/MIR) was made by means of multivariate calibration. The spectral data obtained was also used to extract information about the degree of crystallinity of the recycled resin. Differential scanning calorimetry (DSC) was used as the reference method. Partial least‐squares (PLS) calibration was performed on the MIR and NIR spectral data for prediction of M_n. Four PC factors described fully the PLS models. The root‐mean‐square error of prediction (RMSEP) obtained with MIR data was 360, whereas a RMSEP of 470 was achieved when calibration was carried out on the diffuse reflectance NIR data. A PLS calibration for prediction of degree of crystallinity was performed on the NIR data in the 1100–1900‐nm region, but the ability of prediction of this model was poor. However a PLS calibration in the region 2000–2500 nm yield better results. Four PC factors explained the most of the variance in the spectra and the RMSEP was 0.4 wt %. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 321–327, 2002     

Chemical composition of melamine-urea-formaldehyde (MUF) resins assessed by near-infrared (NIR) spectroscopy

Melamine-urea-formaldehyde (MUF) resins are commonly used in the production of wood-based panels. The composition of the resin influences many properties of the final product. In industrial production, some properties, such as viscosity, pH, solid content, or molar ratio, are assessed after resin production in order to evaluate if they are within the desired parameters. These properties are useful for quality control of amino resins. However, almost no information is obtained if a certain type of reagent or filler is wrongly added to the formulation, even though the resin's final adhesive performance will be affected. Evaluation of the molar ratio of the reagents might be the only of the few industrially used tests capable of making this assessment. Near-infrared spectroscopy (NIR) is a fast and reliable technique for quality control of amino resins and can give a wide range of information regarding chemical composition of these products. This work intends to test the capability of NIR to assess several properties related to MUF resins’ chemical composition. The approach considered two types of problems: 1) whether there was a flaw on resin manufacture process and 2) which raw-material (amount or kind) was incorrectly added to the reactor. Using NIR spectra of a wide range of MUF resins, several models were established to predict the molar ratio of formaldehyde and urea (F/U), molar ratio of formaldehyde and melamine (F/M), molar ratio of formaldehyde and amino groups (F/(NH₂)₂), total urea (% U) and total melamine (% M). These models were constructed using the multivariate technique of Partial Least Squares (PLS) and could successfully determine the properties of a set of industrial resins. The coefficients of variation (CV) obtained were equal or lower than 5%, except for the property of F/M, which was 17%. A more thorough analysis of the established models reveals that spectral components of melamine are harder to extract by PLS than components of formaldehyde or urea.     

Synthesis and spectroelectrochemical investigation of low‐bandgap polymer: Integrated quinoxaline and benzimidazole in one electron acceptor unit

Two novel π‐conjugated monomers, 6‐(4‐octyloxyphenyl)‐4,8‐bis(thiophene‐2‐yl)‐3H‐[d] imidazole[1,2,5] benzothiadiazole (M3) and 4‐(4‐octyloxyphenyl)‐2,6‐bis(thiophene‐2‐yl)‐3H‐[d] imidazole‐acenaphtho[1,2‐b]quinoxaline (M4), were synthesized. The monomer M4 contains a thiophene electron‐donating unit and electron withdrawing unit in which quinoxaline and benzimidazole integrated in one benzene ring. Electrochemical polymerization of the monomers was carried out in acetonitrile/dichloromethane solvent mixture containing tetra‐n‐butylammonium hexafluorophosphate and electrochromic properties of polymers (P3 and P4) are described in this article. Furthermore, the effects of structural difference on electrochemical redox behavior and spectroelectrochemical properties of the two resulting polymers were examined. The results showed that an anodic wave at +0.48 V versus Ag wire pseudo‐reference electrode corresponding to the monomer M4 oxidation was observed, while one anodic wave at +0.70 V was observed in oxidation of M3 as it contains stronger electron withdrawing thiadiazole structure. The UV‐vis‐Near‐infrared (Near‐infrared spectroscopy) (NIR) spectra analysis revealed that the two polymers have one absorbance band centered at 603 nm. The band gaps, defined as the onset of the absorption band at 603 nm of these polymers, were determined as 1.60 eV for P3 and as 1.55 eV for P4. The electrochromic results showed that P3 revealed about 20% optical contrast at 980 nm and the P4 has 30% optical contrast at 806 nm with low response time (1 s for each polymer). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40861.     

Use of postconsumer polyethylene in blends with polyamide 6: Effects of the extrusion method and the compatibilizer

Blends of polyamide and high‐density polyethylene show adequate properties for a large range of applications: they are used for the production of filaments, containers, and molding resins. The effect of the addition of 2 wt % of a compatibilizer, maleic anhydride grafted polyethylene, to the blend was studied and compared to the use of postconsumer polyethylene. The samples were extruded with single‐ and twin‐screw extruders with 25, 50, or 75 wt % f polyethylene, and the test specimens, molded by injection, were characterized by stress–strain tests, thermal properties, and morphologies. Processing the blends with postconsumer polyethylene in both extruders improved the mechanical properties in comparison to the blends processed with high‐density polyethylene and the compatibilizer. The morphologies of these blends showed that there was a decrease in the domain size of the disperse phase with the use of the compatibilizer or postconsumer polyethylene. The results indicate that for this blend, postconsumer polyethylene substituted, with advantages, for the necessity of a compatibilizer and the use of the high‐density polyethylene. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Mid‐IR to Visible Photoluminescence,Dielectric, and Ferroelectric Properties of Er‐Doped KNLN Ceramics

Two mole percentage Er‐doped (K_0.5Na_0.5)_1 ? xLi_xNbO₃ ceramics have been prepared and their dielectric, ferroelectric, and photoluminescence (PL) properties have been investigated. Under an excitation of 980 nm, the ceramics exhibit intense up‐conversion luminescent emission at 548 nm (green), weak emission at 660 nm (red) as well as strong down‐conversion luminescent emission in near‐infrared (NIR) (1.40–1.65 μm) and mid‐infrared (2.60–2.85 μm) regions. Probably due to the induced structure distortion and reduced local symmetry, the PL intensities of the green, red as well as mid‐infrared emissions are enhanced by the doping of Li⁺. Our results show that the Li‐doping is effective in establishing a dynamic circulatory energy process to further enhance the PL intensity of the mid‐infrared emission at the expense of the NIR emission. At the optimum doping level of Li⁺ (~6 mol%), the full bandwidth at half maximum of the mid‐infrared emission reaches a very large value of ~250 nm. The ceramics also exhibit good ferroelectric properties, and thus they should have great potential for multifunctional optoelectronic applications.     

Transparent,Lightweight, and High Strength Polyethylene Films by a Scalable Continuous Extrusion and Solid‐State Drawing Process

The continuous production of transparent high strength ultra‐drawn high‐density polyethylene films or tapes is explored using a cast film extrusion and solid‐state drawing line. Two methodologies are explored to achieve such high strength transparent polyethylene films; i) the use of suitable additives like 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐ditertpentylphenol (BZT) and ii) solid‐state drawing at an optimal temperature of 105 °C (without additives). Both methodologies result in highly oriented films of high transparency (≈91%) in the far field. Maximum attainable modulus (≈33 GPa) and tensile strength (≈900 MPa) of both types of solid‐state drawn films are similar and are an order of magnitude higher than traditional transparent plastics such as polycarbonate (PC) and poly(methyl methacrylate). Special emphasis is devoted to the effect of draw down and pre‐orientation in the as‐extruded films prior to solid‐state drawing. It is shown that pre‐orientation is beneficial in improving mechanical properties of the films at equal draw ratios. However, pre‐orientation lowers the maximum attainable draw ratio and as such the ultimate modulus and tensile strength of the films. Potential applications of these high strength transparent flexible films lie in composite laminates, automotive or aircraft glazing, high impact windows, safety glass, and displays.     

Surface roughness effect on optical loss in waveguide using isotropically induced crosslink network of siloxane–polyimide copolymer

Optical properties of two-fluorinated polysiloxane-co-polyimide (PI-PDMS and 3-(aminopropyl)triethoxysilane [PI-APTES]) were investigated based on their molecular structure and compared with the pure PI at 1,550 nm radiation. The refractive indexes and birefringence of the copolymers were reduced which is attributable to the chain flexibility as substantiated from the differential scanning calorimetry result. They are highly transparent at near infrared (NIR) region with light transmittance above 90% at visible region while displaying excellent thermal stability up to 456°C. Asymmetry planar waveguides was fabricated which recorded a respectable low optical loss 0.020 dB/cm for pure PI, 0.042 dB/cm for PI-PDMS, and 0.066 dB/cm for PI-APTES, respectively. Despite proving low NIR absorption and low birefringence, extrinsic factor namely surface roughness was accounted as affecting the higher optical loss in polyimide siloxane copolymer compared to pure PI. The excellent thermal and optical properties displayed by these series of material established their viable application as waveguide material at 1,550 nm wavelength.     

One‐step dyeing of polyethylene terephthalate fabric,combining pretreatment and dyeing using alkali‐stable disperse dyes

In the conventional dyeing process, polyester and its blended fabrics are usually dyed in a weak acidic medium. In order to reduce cost and improve production efficiency, a new dyeing method – one‐step dyeing of polyethylene terephthalate fabrics, combining pretreatment and dyeing in alkali conditions – was investigated. The alkali‐stable disperse dyes Red 900, Red 902, Yellow BROB and Blue 825 were used to dye polyethylene terephthalate fabrics. The dyeing properties of polyethylene terephthalate fabrics in the case of one‐step dyeing at various pH values or sodium hydroxide concentrations were discussed in terms of colour yield, colour parameters and fastness. The performance of one‐step dyeing using alkali‐stable disperse dyes was excellent. The dyed fabric had good fastness. Wet processing could be combined and shortened. One‐step dyeing of polyethylene terephthalate fabrics could reduce the consumption of water and energy and improve production efficiency. One‐step dyeing of polyethylene terephthalate has potential application in cleaner textile production.