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Monitoring of polymer melt processing

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2010 Meas. Sci. Technol. 21 062001 (http://iopscience.iop.org/0957-0233/21/6/062001) View the table of contents for this issue, or go to the journal homepage for more

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IOP PUBLISHING Meas. Sci. Technol. 21 (2010) 062001 (19pp)

MEASUREMENT SCIENCE AND TECHNOLOGY

doi:10.1088/0957-0233/21/6/062001

TOPICAL REVIEW

Monitoring of polymer melt processing

Ingo Alig1 , Bernd Steinhoff and Dirk Lellinger
Deutsches Kunststoff-Institut, Schlossgartenstrasse 6, D-64289 Darmstadt, Germany E-mail: ialig@dki.tu-darmstadt.de

Received 13 November 2009, in nal form 15 February 2010 Published 16 April 2010 Online at stacks.iop.org/MST/21/062001 Abstract The paper reviews the state-of-the-art of in-line and on-line monitoring during polymer melt processing by compounding, extrusion and injection moulding. Different spectroscopic and scattering techniques as well as conductivity and viscosity measurements are reviewed and compared concerning their potential for different process applications. In addition to information on chemical composition and state of the process, the in situ detection of morphology, which is of specic interest for multiphase polymer systems such as polymer composites and polymer blends, is described in detail. For these systems, the product properties strongly depend on the phase or ller morphology created during processing. Examples for optical (UV/vis, NIR) and ultrasonic attenuation spectra recorded during extrusion are given, which were found to be sensitive to the chemical composition as well as to size and degree of dispersion of micro or nanollers in the polymer matrix. By small-angle light scattering experiments, process-induced structures were detected in blends of incompatible polymers during compounding. Using conductivity measurements during extrusion, the inuence of processing conditions on the electrical conductivity of polymer melts with conductive llers (carbon black or carbon nanotubes) was monitored.
Keywords: process monitoring, in-line, on-line, polymers, micro and nano composites, melt

processing, extrusion, mould injection, UVvis, NIR, ultrasonics, light scattering, dielectric spectroscopy (Some gures in this article are in colour only in the electronic version)

1. Introduction
Over the last two decades economic, legislative and environmental demands have increased more and more. The same holds true for the need to ensure consistent quality of the nal products. These issues are of specic relevance for the pharmaceutical industry, where the socalled process analytical technology (PAT) has been developed to help companies improve conformity with manufacturing compliance regulations. Similarly, for processing of polymers, requirements with respect to productivity and quality become more and more important [1] and can be fullled by implementing PAT tools for real or nearreal-time measurements of chemical composition and/or physical properties as components of quality management
1

Author to whom any correspondence should be addressed.

systems. Such measurements yield data for control and optimization of material properties and processing conditions. Furthermore, they provide the possibility of improving process understanding and allow generating input data for process simulation or for validation of the simulation results. PAT generally differentiates between in-line, on-line and off-line measurements. In-line measurements are implemented directly within the processing line, resulting in very short (or even nonexistent) delays for sampling. However, in-line sensors may interfere with the main process and the sensors can be inuenced by the temperature or pressure. On-line techniques require a sampling stream to be diverted from the process ow line and transferred to the measurement device. Thus, the latter is isolated from the main stream which simplies maintenance work. On the other hand, delays might occur due to material storage in the bypass [1].
1
2010 IOP Publishing Ltd Printed in the UK & the USA

0957-0233/10/062001+19$30.00

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Topical Review

Off-line analyticswhich still dominates process analysis is usually cost intensive and leads to large delays between the occurrence of defects or process instabilities and their detection. A comprehensive discussion of the different process control schemes can be found in [2]. Classical process control based on in-line measurements of conventional parameters such as temperature and pressure is in many cases not sufcient to account for processinduced variations in material properties or to guarantee stable processing within a given process window. This is especially the case for complex polymer systems [3]. Accordingly, polymer industry is more and more interested in fast, reliable and robust in-line methods, providing direct information on chemical composition or material properties. In general, polymer systems can be subdivided into thermoplastic materials, elastomers and thermosets. Since the processing methods for all three classes are different, we focus in this report on methods for monitoring melt processing of thermoplastic polymers. Compounding of formulations by melt mixing using extruders is an important step in thermoplastic processing. This means that additives or llers are incorporated into melts of the basis polymers. In polymer industries, a broad range of additive types, fullling different requirements such as protection against UV, heat or oxygen, are used to tune the material properties for a given application. Almost all commercial polymers containat least in small amountsadditives soluble in the polymer, or llers. Fillers can consist of micro- or nano-sized particles dispersed in the polymer matrix. Compounding is also used to produce polymer blends of two or more polymers in order to combine the properties of different polymers (or simply to reduce costs). Interesting properties which can be inuenced by blending or adding modiers or llers are mechanical, thermal or electrical properties or melt ow characteristics. Since the nal properties of blends or compounds containing llers are largely determined by the morphology of the blend domains or the quality of the ller dispersion, respectively, there is considerable demand for monitoring the morphology during compounding. Due to the generally high viscosity of polymer melts, mass and thermal transport and thus mixing and possible chemical reactions are strongly hindered during processing and must be forced by mechanical energy. Here extruders are the established processing units. The melt leaving the extruder is quenched and the solid material thus obtained by vitrication or crystallization is pelletized. The pellets can be processed into nal components by injection moulding. In addition to compounding, extruders are also used to produce goods such as tubes, hoses, window frames, plates and lms. This report concentrates on compounding of thermoplastics, where the major part of process monitoring-oriented research has been done until now. Much less effort has been spent on injection moulding or deep drawing. The currently available in-line methods for compounding, extrusion and mould injection can be subdivided into three groups: (i) methods which provide information on the state of process (not topic of this report), (ii) methods which are mainly sensitive to the chemical composition and (iii) methods
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which provide morphological information such as quality of ller dispersion, agglomeration or domain size and shape in polymer blends. Excellent papers regarding in-line monitoring of chemical composition already exist in the literature and, therefore, are summarized only briey in section 2. As yet, not much work related to obtaining morphological information by in-line or on-line control (iii) exist. Therefore, section 3 will expand recent research on morphology monitoring.

2. Monitoring techniques
2.1. Overview Already in the rst application of PAT to polymer processing, it has been noted that a simple transfer of laboratory instrumentation into the process is not sufcient for most applications. Implementation of process measurement devices requires in most cases reduction of data acquisition time, while maintaining a sufcient signal-to-noise ratio and resolution even in harsh production environments [4]. Furthermore, sensors for monitoring melt processing of thermoplastic polymers will be operated at temperatures well above the melting or glass transition temperature of the polymer. This requires sensors with long-term stability at temperatures between 180 and 350 C and the ability to withstand pressures up to 300 bar as well as corrosion and abrasion by llers. Finally, the nancial resources for process monitoring (development, equipment, maintenance) in the industry are limited due to the relatively low added value in classical polymer production as compared to pharmaceutical products. A somewhat arbitrary overview of the methods that in principle are suitable for in-line monitoring of polymer processing is shown in gure 1. Many of these methods were tested so far for monitoring of polymer melt compounding. As stated above, pressure and temperature are the classical quantities for polymer process control. Furthermore, viscosity is measured for quality control of formulation batches in some cases on-line. For this purpose, commercially available slit die rheometers are used. In excellent papers of Coates et al ([3] and references therein), actual developments of in-line monitoring techniques for analysis of melt processing are described. Different techniques such as rheometric, optical, ultrasonic and electrical methods have been used successfully to gain information about the physical properties and chemical composition of polymer melts [5]. Therefore, in the following only a brief review of the methods for monitoring chemical composition and material properties is given. The rst part will focus on extrusion monitoring. In the nal part of this section some developments for in-line control of injection moulding are revised briey. Actual examples for the scattering methods in gure 1 will be given in section 3. 2.2. Extrusion monitoring: properties and chemical composition Beside optical (mainly NIR) spectroscopy, ultrasonic spectroscopy is one of the classical techniques for in-line

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Topical Review

Figure 1. Methods for in-line monitoring of polymer processing.

control [3, 648]. The potential of the method is given by the direct measurement of a mechanical property, the robustness of the sensor especially against abrasion and high pressure and the relatively low costs for the equipment. Since the beginning of the 1980s, ultrasonic measurements have been applied to many polymeric systems during processing, including polymeric foam [20, 45] and thermoset processing [22, 24]. In-line measurement of the electrical conductivity or specic resistivity is another technique which probes directly a physical property of practical relevance. For frequencydependent measurements of the electrical conductivity or dielectric permittivity, the method is called dielectric relaxation spectroscopy (DRS). Other common notations are impedance or conductivity spectroscopy. In [40, 42, 43, 4964] applications of in-line conductivity measurements (or DRS) during polymer processing are described. Ac and dc conductivity or permittivity measurements have been applied for monitoring of conductive ller content (carbon black and carbon nanotubes) and ller dispersion (including nanoller). In gure 2, an example of our work on extrusion monitoring by in-line conductivity measurements is shown. The dependence of the conductivity of a polycarbonate (PC) melt containing multi-walled carbon nanotubes (MWCNT) [64] on processing conditions was studied during extrusion using the slit die shown in gure 3. In this die, insulated electrodes in the plate capacitor geometry are implemented. The die is attached to the outlet of an extruder. During extrusion of the PC/MWNT melt, the conductivity is very low, since the conductive ller network is destroyed by the shear and elongational ow. In the quiescent melt, after the stopping of the extruder, the conductivity recovers by reformation of the conductive ller network. Optical spectroscopic techniques (Raman, IR, NIR, UV visible or uorescence) as analytical tools for chemical quality control during melt processing are used to extract specic molecular information or information on chemical composition. These methods are interesting especially for monitoring of complex polymer systems and when reactions occur during processing [3].
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Figure 2. In-line conductivity measurement of a polycarbonate/carbon nanotube composite during melt extrusion at different melt temperatures (screw speed: 175 rpm) and in the quiescent melt after the extruder has stopped. Indication for shear-induced destruction and conductivity recovery [64].

Figure 3. The two half shells of a dielectric measurement die with rectangular electrodes insulated by a ceramic inlay [64]. After mounting, the two electrode areas are face to face.

IR spectroscopy (Fourier-transform infrared spectroscopy: FT-IR) has been used in analytical laboratories for

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Topical Review

decades. It was the rst optical spectroscopic method that was tested for controlling melt extrusion. Fritz and Ultsch [65] applied on-line FT-IR to monitor reactive extrusion where polyethylene was grafted with organosilanes. With a gear pump, a small fraction of the melt was drawn continuously to a process spectrometer [66, 67] equipped with a special transmittance measurement cell of adjustable path length [68]. Application of similar online instrumentation is described in [6, 69, 70]. In [70], in-line FT-IR was tested also to monitor the copolymerization of the styrenemaleic-anhydride model system with an alky-amine during melt extrusion. A ZnSe-attenuated total reection (ATR) probe was mounted in the crotch region between the screws of a twin screw extruder. Despite the fact that FT-IR delivers detailed vibrational spectra which usually can be well correlated with the chemical composition, the method has several drawbacks. Strongly absorbing melts require the path length to be as small as 50 m for FT-IR transmission measurement [66]. Thus, these measurements are mainly restricted to on-line congurations using a bypass. A pronounced delay is caused by the time it takes to replace the volume in the bypass and the narrow measurement cell by the viscous melt. In-line FT-IR by an ATR probe likewise suffers the problem of high melt viscosity. The penetration depth of IR in the melt in an ATR measurement is only about 1.5 m [70] and the exchange of this thin layer of high viscous material likewise takes time [70]. Last but not least, optical bre technology for the mid IR spectral range is still very expensive and susceptible to damage. Development of robust equipment for NIR, Raman, UV vis and uorescence spectroscopy has promoted the use of these methods to monitor polymer processes in an industrial environment. Progress was made in high-temperature and high-pressure probes, robustly designed spectrometers (moving dispersive elements replaced by array detectors) and bre optical technology [1, 3, 6]. Using bres for UVvis or NIR, the spectrometer can be placed dozens of metres away from the melt processing units. Examples of high-temperature and high-pressure probes for optical spectroscopy are shown in gure 4 together with an ultrasonic transducer. For extrusion monitoring the probes are usually mounted on a measurement adaptor (see gure 4 also). As with the dielectric die (gure 3), this measurement adaptor exhibits a rectangular melt channel and is attached to the outlet of the extruder (gure 5). Probes for different methods are mounted along the melt channel for parallel operation. Although such an assembly is not typical for industrial in-line application, it allows fast and easy comparison of the performance of different measurement techniques and a selection of the most suitable one (or combination) for a given monitoring problem. Probes of other methods can be mounted as well. Compared to IR spectra, the band structure of a NIR spectrum is less detailed. The overtone and combination bands observed arise only from certain molecular groups (mainly CH, OH and NH bonds), and the peaks show considerable overlap. Thus quantitative analysis is more difcult. As an example, diffuse reectance NIR spectra
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Figure 4. Raman, NIR and ultrasonic (US) sensors. A measurement adaptor (slit die) is partially shown on the left side.

Figure 5. Scheme of a twin screw extruder (left) equipped with a measurement slit die with different sensors (right). US: ultrasonic probes. p, T: pressure and temperature.

Figure 6. Diffuse reectance NIR spectra of POM modied with different amounts of TPU (as indicated in the plot).

of polyoxymethylene (POM) melts modied with different amounts of thermoplastic polyurethane (TPU) are shown in gure 6. The diffuse reectance measurements were calibrated with a white standard, a wavelength-independent strong diffuse reecting sample. Since the diffuse reection of pure POM is much weaker compared to the white standard, the average absorbance increases with decreasing TPU content. Only the small peak at about 1490 nm gives a direct signature of the increasing TPU content in the spectral shape.

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Figure 7. Cross validation plot of the chemometric model tted to the diffuse reectance NIR spectra shown in gure 6.

Figure 8. UVvis transmission spectra of PLA as a function of the screw speed.

2.3. Injection moulding The information contained in such not well-pronounced spectra can be exploited by multivariate methods (chemometrics) [72, 73] yielding a calibration model. This model is used to predict the chemical composition from a measured spectrum. Such a calibration model was created using partial least-squares analysis (PLS) for the spectra shown in gure 6. Actually, for each composition ten spectra were recorded. The 70 spectra in total form the so-called training set. A measure for the quality of a calibration model is obtained by cross validation. The spectra belonging to the samples with one concentration, e.g. those with 5% TPU content (here ten spectra), are left out and the model is calculated with the remaining spectra. Next, the concentrations corresponding to the spectra not included in the model just produced are predicted. This procedure is repeated for all samples, and the predicted concentration is plotted as a function of the actual concentration (cross validation plot), gure 7. The availability of fast computers has promoted the use of chemometrics. It has since been applied to almost any type of spectra (see e.g. [43] and section 3.3 in this text). A number of studies for extrusion monitoring have been presented in the literature using NIR in transmission and reectance [3, 6, 7, 40, 42, 43, 46, 48, 71, 7485], Raman spectroscopy [3, 6, 7, 30, 42, 43, 46, 8689], UVvisible spectroscopy [9092] and uorescence spectroscopy [3, 9399]. Recently, we applied multivariate analysis also for prediction of the ller content by ultrasonic attenuation spectroscopy [47]. In-line UVvis spectroscopy can be useful to monitor process-induced degradation in polymer melts. An example is given in gure 8. An experimental setup similar to that shown in gure 5 was used to measure the UVvis transmittance of a polylactide (PLA) melt as a function of processing conditions [92]. In gure 8 it can be seen that with increasing screw speed, the UV-absorption edge moves into the longer wavelength region (red shift). This mirrors increasing degradation. The absorption below 400 nm can be recognized visually as yellowing.
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Ultrasonic techniques to monitor injection moulding are described in [13, 100, 101]. Measurements of in-line nozzle melt pressure and hydraulic injection pressure are discussed in [102]. Performing conductivity measurements during injection moulding is also rare. It is restricted to polymers containing conductive llers such as carbon black (CB) or carbon nanotubes (CNT) [103, 104]. Further examples are reported for in-line monitoring of the resin transfer moulding process [105, 106]. An example [104] for a conductivity measurement during injection moulding is shown in gure 9. The in-line measured conductivity values (open squares in gure 9) for the polycarbonate/styrene-co-acrylnitrile blend (Bayblend R ) containing 4 wt% multi-walled carbon nanotubes are compared to the off-line measured values (open circles) for different injection conditions. The mould, the plastic part and the sensor are schematically shown in gure 10. For the in-line measured conductivity, the values recorded 9 s after the start of injection were taken. The good correlation between in-line and off-line data demonstrates the potential of in-line conductivity measurements. The tremendous decrease of the conductivity with increasing injection speed and decreasing temperature can be explained by the destruction of the conductive ller network due to shear stress resulting from increasing shear rate or viscosity, respectively. The mould temperature seems to have only minor inuence. Optical methods had also been tested for in-line monitoring of injection moulding. Such work is described in Bur et al [107] and Thomas and Bur [108110]. In [107], a bre optical sensor was attached to the mould cavity to monitor the uorescence intensity of polymers doped with an appropriate uorescent dye during cooling and subsequent solidication. The onset of solidication could be detected and correlated with temperature. Transmittance measurements in the mould are correlated with crystallization behaviour of polypropylene in [108, 109], while in [110] the product shrinkage is monitored in situ. In [111], transmittance NIRspectroscopy with the probes mounted on the nozzle was successfully tested to identify colour changes and moisture in the melt.

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Topical Review

Figure 9. Inuence of injection speed (left), melt temperature (middle) and mould temperature (right) on the in-line (squares) and off-line (circles) measured electrical conductivity of a polycarbonate/styrene-co-acrylnitrile blend containing 4 wt% MWCNT.

Figure 10. Scheme of the mould, the plastic part and of the conductivity sensor.

3. Morphology control
3.1. General considerations In the context of polymer materials, the term morphology is related to heterogeneous systems such as (i) composites with ller particles, (ii) immiscible polymer blends of two or more components and (iii) semi-crystalline polymers. Since the focus of this report is melt processing, semi-crystalline morphology, appearing during cooling, will be not considered. Classical polymer composites contain llers such as chalk or talcum with typical particle sizes in the micrometre region and typical ller contents of about 40 wt% and more. The particles in so-called nanocomposites are of sub-micron size from about 10 nm up to several hundred nanometres. Typical ller concentrations in nanocomposites are in the order of 5 wt% or less. In binary polymer blends, the content of one of the components varies typically between 20 and 80 wt%. In special applications, the content can be in the region of some per cent. The domain size in polymer blends ranges from about hundred nanometres to dozens of micrometres. The nal properties of polymer compounds such as mechanical modulus, stiffness, toughness or scratch resistance are known to depend strongly on the degree of ller dispersion, particle size and size distribution. For polymer blends, the relevant parameters are size and shape of the
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domains. Therefore, morphology control during polymer melt processing of compounds and polymer blends is highly desired. This is especially the case for nanocomposites, where even small amounts of nanollers can enhance the properties tremendously. Therefore, optimum dispersion of the llers has to be ensured. Also related to morphology is the detection of discrete impurities in otherwise homogeneous polymers. Such impurities, which typically occur statistically, are referred to as spots, burners or gel particles. They can reduce the optical quality of the nal product or can act as hot spots causing initiation of defects. Their sizes vary typically from 0.1 to 1 mm. Sometimes much smaller particles at the size of some microns or nanometres can also be relevant if their number density is high enough so that the material becomes turbid or agglomerates are formed. Monitoring of those impurities during extrusion is reviewed in section 3.5. Classical ways of fast morphology control are inline, off-line or at-line turbidity measurements at a single wavelength. This approach is well described in the literature (see e.g. references cited in section 3.2) and the equipment is commercially available. In addition, it is well known that the analysis of the angle-dependent scattering of electromagnetic or acoustic waves can provide information on particle size and shape (form factor) as well as particle arrangement (structure factor). Thus, angle-dependent static and dynamic light scattering experiments are well established in laboratory analytics for polymer solutions and colloidal systems [112]. Angular-dependent static light scattering techniques are also common for in-line, on-line or at-line particle sizing (laser diffraction techniques) of wet and dry production streams e.g. in pharmaceutical industry, cement production or metal powder atomization. Their application to polymer melt processing is still limited. This might be due to the difculties of installation under the harsh conditions of melt processing and the extensive data analysis required. Furthermore, limitations arise because of too strong scattering of melts of polymer blends or composites, often preventing reliable data analysis because of strong multiple scattering. In section 3.4, the state-of-the-art for in-line small-angle light

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scattering during compounding is reviewed and an example for monitoring of extrusion of a binary melt is given. Interesting alternatives to angle-dependent scattering methods for morphology control are the detection of absorption spectra. For such measurements, commercially available process spectrometers and probes can be used in simple transmission or reection geometry. Ultrasonic spectroscopy is indeed already used for on-line particle sizing (e.g. on ore slurries [113]). Examples for the application of optical and ultrasonic spectroscopy to obtain information on particle size and size distribution in composite polymer melts during extrusion are reported in sections 3.2 and 3.3, respectively. Optical as well as ultrasonic absorption spectra were correlated with the size of ller particles obtained from scanning electron microscopy (SEM) or x-ray micro-computer tomography (-CT). 3.2. Morphology control by optical spectroscopy 3.2.1. Turbidity and spectroscopic measurements: previous work. In [114], turbidity measurements at a single wavelength were used to obtain information on particle size during polymer latex production. For data analysis, the measured turbidity was compared to simulated turbidity data using Mie theory. Besides the measured turbidity, the number density of particles is required. In [114], the latter was obtained via determining the mass fraction of latex particles in the reactor, and the density values of the latex and the dispersion. In [62], the turbidity was used to get a measure of the number density of agglomerates remaining in a polymer melt after compounding of nanollers. For the theoretical calculation of the turbidity, an average diameter of the agglomerates was assumed. Both examples show the principal difculty of the analysis of single wavelength turbidity data. In addition to the refractive index values for Mie calculations, the number density of particles or, vice versa, the particle size as additional sample information is required. In the literature, NIR [115, 116], UV and NIR [117] and Raman spectroscopy [118] were tested for their ability to size latex particles in polymer dispersions. By use of chemometric analysis, the recorded optical spectra were correlated with the size of the latex particles obtained by dynamic light scattering or scanning electron microscopy (SEM). Since the as-recorded spectra contain chemical and morphological information, they are only indirectly related to the particle size. Therefore, even a slight change of the chemical composition (of matrix or ller) requires a new calibration of the chemometric model. Only the scattering background within the optical spectra is directly related to morphology. In the case of heterogeneous materials (e.g. compounds containing ller particles or phase domains in blends), the optical spectra (here UV/vis and NIR) contain a contribution due to light scattering on the inhomogeneities. Therefore, the analysis of the shape of the so-called background scattering curve can provide direct information on average particle size and number density. For quantitative analysis (see section 3.2.3), the background scattering curve has to be separated from the chemical information (i.e. specic absorption bands of the
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components). This wavelength dependence of the scattering contribution has been used already in colloid science for probing the particle size of colloids [119121]. 3.2.2. In-line experiments on polymer melts with nanollers. As stated above, optimum dispersion of nanollers is often crucial to achieve the desired material properties of polymer nanocomposites. To get information on the degree of dispersion of nanollers during melt compounding, UV/vis and NIR-transmission spectroscopy were used on polymer/clay nanocomposites. For these experiments, pairs of UV/vis and NIR probes (transmission mode) were attached to a rectangular slit die. The height of the melt channel (i.e. sample thickness) was 4 mm [40, 122]. The clay (montmorillonite) consists of stacks of silicate platelets. The platelets are some nanometres thick and have lateral dimensions in the order of 100 nm. The dispersion mechanisms of the clay are intercalation (polymer molecules are arranged between the platelets of a stack) and exfoliation (random distribution of individualized platelets within the polymer matrix) [123, 124]. Large agglomerates of clay particles may exist as well. Since the wavelengths in the optical (UV/vis/NIR) region are considerably larger than the mean particle size of exfoliated clay, the spectra do not allow a direct differentiation between intercalation and exfoliation. However, the spectra can be used as an indirect probe for the nanoparticle dispersion, because the scattering contribution in the optical range decreases with decreasing number and/or size of remaining agglomerates: The smaller the average size of the remaining agglomerates (containing several platelet stacks), the more intercalation or exfoliation has occurred. Regarding the monitoring of agglomerates, this approach is analogous to the work in [62]. Figure 11 shows as an example the in-line monitored NIR absorption spectra of pure polystyrene (PS) melt together with a typical spectrum of a PS melt containing 5 wt% of clay. The polystyrene (PS168N) was a product of BASF SE (Germany) and the clay (Nanol SE3010) was provided by S ud Chemie AG (Germany). The NIR spectrum of the pure polymer shows the specic absorption bands of PS. For the PS/clay composite, the PS bands are superimposed by an additional contribution from light scattering by the particles (scattering background: bold line in gure 11). In optical spectroscopy, this scattering background is usually removed to extract information on the chemical structure and/or composition from the absorption bands. On the other hand, to obtain morphological information, the absorption bands have to be removed and the scattering background has to be analysed. The scattering background (difference absorbance spectrum: A) can be extracted with adequate accuracy by subtracting the spectrum of the pure polymer. Details for the data analysis are given in section 3.2.3. The difference spectra A from NIR and UV/vis spectroscopy can be combined to form a single UV/vis/NIR difference spectrum. Such spectra of a PS/clay composite with 5 wt% clay as a function of the screw speed are shown in gure 12. It can be seen that the difference absorbance A decreases with increasing screw speed, indicating decreasing

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modes of polymer and ller, respectively. N is the number density of the ller particles. Csc () is the scattering cross section of the particles in the melt. For a transmission measurement, Csc () is virtually an absorption coefcient, since the transmitted intensity is reduced due to the scattering. For the limiting case of a pure polymer melt, wP has a value of 1 and all contributions from the ller are zero. Subtraction of the absorption spectrum of the pure polymer melt from equation (1) yields the difference absorption spectrum A(): A() = s((wP 1)P () + wf f () + N Csc ()). (2) In gures 11 and 12, it can be seen that the difference absorption spectra are smoothly shaped without obvious reminiscences of band structure. Therefore, the contributions of (wP 1) P () and wf f () can be assumed to be very small. For the practical purpose of process monitoring, the rst two terms in equation (2) can be neglected in most cases and the difference spectrum reveals the scattering background (3): (3) A() = sN Csc () = s (), where is the turbidity. This approach, however, is limited to llers with low optical absorption. For uniform spheres, the angular scattering properties and thus the scattering cross section Csc (), which is the integral of the angular scattering, can be calculated rigorously by Mie theory [121, 126, 127]. Filler particles usually do not exhibit a uniform and well-dened shape. For the actual system, the agglomerates and the intercalated clay stacks are irregularly shaped with an aspect ratio close to 1, while exfoliated clay consists of very thin platelets. Nonsphericity has pronounced effects on the angular scattering but, as stated in [125], much less effect on the scattering cross section of randomly oriented asymmetric particles. Therefore, as a rst approximation, the experimental results can be interpreted in terms of scattering of spherical particles with diameters corresponding to the shape-averaged particle size. The agglomerates, which dominate the scattering in the composite melt, exhibit a shape close to spherical anyway, while the platelets will hardly contribute to the scattering due to their small thickness. Multiple scattering, a common problem for angular-dependent scattering in concentrated systems, is here of minor importance, since transmission measurements are identical to turbidity measurements at different wavelengths, which are almost insensitive to multiple scattering [128130]. In order to illustrate the inuence of particle size on the optical spectra, scattering cross-section curves calculated by Mie theory [121, 126, 127] are shown for spheres with radii of 500 nm and 2 m in gure 13. The smaller radius value was taken as representative for the shape-averaged particle sizes of exfoliated and intercalated clay and the latter for large agglomerates. The wavelength ranges of the UV/vis and NIR spectrometer used are indicated. A computer program described in [131] was used for the simulation. The input parameters are radius and refractive index of the sphere as well as the refractive index of the matrix. For the latter, the typical value for the polymer matrix of 1.5 was assumed. The clay is chemically similar to quartz, exhibiting a refractive index of 1.45. These values were taken for the calculations.
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Figure 11. NIR absorption spectra of PS and a PS/clay melt recorded during extrusion at 210 C (screw speed 450 rpm, throughput 5 kg h1 ). The bold line (arrow) represents the scattering background of the PS/clay nanocomposite calculated by subtraction of the spectrum of pure PS.

Figure 12. Combined UV/vis/NIR difference spectra (after subtraction of the PS spectrum) as a function of the screw speed for a PS/clay composite (5 wt% clay). The barrel temperature was TB = 210 C and the throughput was Q = 5 kg h1 .

scattering contribution. This qualitatively reects the better dispersion of the clay with increasing screw speed, but does not provide direct information on average particle size. 3.2.3. Extracting morphological information from optical spectra. The following analysis of the optical spectra is based on LambertBeers law. A linear mixing law is assumed for the absorption coefcients of the polymer matrix P () and the ller F (). Furthermore, a linear superposition of the specic absorption bands, the scattering background and the apparatus function is assumed. Consequently, the measured (apparent) absorption A1 () of a polymer/(nano)composite melt can be described by A1 () = lg(I0 ()/It ()) = s(wP P () + wf f () + N Csc ()) + a () (1) where I0 () and It () are the incident and transmitted intensities. a () is the absorption (apparatus function) caused by the probes, the optical bres, etc, s is the thickness of the polymer melt and wP and wf are the weight fractions of polymer and ller, respectively. P () and F () are related to the UV/vis electronic transitions and the NIR vibration

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Figure 13. Scattering cross section Csc () as a function of the wavelength. Theoretical calculation for spherical particles (Mie scattering).

Figure 14. Plot of the Csc ()/ Csc () curves corresponding to the theoretically obtained curves shown in gure 13 for the wavelength range of 4301625 nm.

In gure 13, it can be seen that the scattering cross section increases tremendously with particle size. The maximum value of the Csc () curve is roughly proportional to the square of the particle radius. Furthermore, with increasing particle size, the position of the maximum of the scattering curve shifts to larger wavelength values. Since the number density N of the agglomerates contributing to scattering is usually not known, the scattering cross section of the particles Csc () cannot be calculated from the measured difference absorption A() by equation (3). Therefore, no direct information on particle size can be obtained by this approach. However, the factor N cancels out by introducing a normalized scattering cross section Csc ()/ Csc () for a wavelength interval from min to max , where Csc () is dened max Csc () d/(max min ). In the by Csc () = min experimental wavelength range, Csc ()/ Csc () is equal to the measured normalized difference absorption spectrum A()/ A() : A()/ A()
min ,max

Figure 15. Plot of the experimentally obtained A()/ A() curves for PS/clay, as calculated from the curves shown in gure 12 using equation (4) for the wavelength range of 4301625 nm. Barrel temperature and throughput are given in gure 12.

A()min ,max
max min

A() d/(max min ) (4)

= Csc ()/ Csc () .

Replacing A() in equation (4) with the simulated Csc () curves from gure 13, the normalized scattering cross section for spherical particles of 500 nm and 2 m can be calculated correspondingly. In order to compare the simulated curves with the experimental spectra, in gure 14 Csc ()/ Csc () was calculated for the experimental available UV/vis/NIR wavelength range from min = 430 nm to max = 1625 nm. From the curves for the two particle sizes, it can be seen that the smaller the (average) particle size, the more pronounced the variation of Csc ()/ Csc () with wavelength. This yields the possibility of extracting information on both number density of scatterers and mean particle size from the scattering spectrum, even for a limited wavelength range. 3.2.4. Correlation between processing conditions and ller dispersion. The A()/ A() curves are calculated
9

(equation (4)) from the combined UV/vis/NIR spectra shown in gure 12 and are plotted in gure 15. From comparison with the simulated curves in gure 14 it can be concluded that a steeper decay of the curves in gure 15 indicates a smaller (averaged) particle size due to a better dispersion at higher screw speeds. This agrees well with x-ray -CT images from the extruded strands in gure 16, which shows that the number of huge agglomerates (size > 10 m) decreases with increasing screw speed. This results in decreased averaged particle size. A series of compounding experiments with different polymers (polyamide-6, PA6 and poly-butyleneterephthalate, PBT) and varying processing conditions (screw speed, throughput, melt temperature) conrm that the optical spectra correlate quite well with the weight content wb (per cent of clay net weight) of remaining huge agglomerates (radius > 10 m) in the composite. The values for wb were obtained by analysing -CT and optical microscopy images with the ImageJ software (version 1.37v, http://rsb.info.nih.gov/ij/). The solid line in gure 17 represents an empirical relationship (quadratic polynomial) between wb and the value of A()/ A() (gure 15) at 450 nm. At rst glance, the good correlation between the content of agglomerates and normalized difference absorption

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[119, 120] for polymer latex dispersions, where the scattering curves were correlated with particle size by use of a loglog plot of the turbidity versus wavelength. Such a plot delivers for at least a sub-interval of wavelengths a straight line. The slope was correlated with theoretical calculations (Mie theory) for spherical particles. 3.3. Morphology control by ultrasonic spectroscopy 3.3.1. Sound scattering on llers. In contrast to the nanocomposites considered in the preceding section, traditional polymeric composites contain large amounts (e.g. 40 wt% and higher) of micron-sized particles such as chalk or talcum. The particle size in those composites should be in the range of 1 to 10 m and agglomeration has also to be prevented. Agglomerates with a size of dozens of microns up to some 100 micrometres can reduce material properties. In such melts, the turbidity is usually too high for optical transmission measurements. Performing (diffuse) reection measurements is possible in principle, but the scattering contribution within the spectra (scattering background) does not show a signicant wavelength dependence, since at such high concentrations of micron-sized particles strong multiple scattering occurs and smears out any wavelength dependence. Due to the much larger wavelength of ultrasonic waves, the situation is different for ultrasonic spectroscopy, and it was shown that this technique can be used to monitor the content and quality of dispersion of microllers in polymer melts during extrusion. This has been tested for polypropylene (PP)/chalk composites using a pulse transmission setup (thickness of the melt channel 4 mm) during extrusion [47]. In such melts, the contribution of the polymer matrix to ultrasonic absorption can practically be neglected, and, therefore, the sound attenuation in the PP/chalk melts is dominated by scattering of the ultrasonic waves on the ller particles. This is in analogy to the scattering contribution of the nanoparticles in the optical absorption spectra shown in section 3.2. Also in analogy to the Mie theory for scattering of optical waves by spherical particles, there exist similar formalisms for acoustics [132, 133]. In gure 18, the theoretically calculated ultrasonic attenuation for spherical chalk particles (with diameter of 80, 100, 150 and 200 m) is plotted as a function of the frequency. For ultrasonic wavelengths = c/f (c is the sound velocity and f is the frequency) in the order of magnitude of the particle diameter, a maximum appears in the ultrasonic attenuation spectra due to sound scattering. This is similar to the maximum in the scattering cross section of optical spectra in gure 13. For particles with diameter well below the wavelength 0 of the central frequency of the transducers (f0 = 5 MHz, 0 = 200 m) only a monotonic increase of the attenuation with increasing frequency can be seen. Larger particles (d 100 nm) cause a maximum which shifts to lower frequency with increasing particle size. Therefore, measurements of the frequency-dependent ultrasonic attenuation can be used for in-line monitoring of particle size and dispersion in the micrometre range. It has to be stated that ultrasonic in-line measurements are not limited to optical transparent samples and that the experimental assemblies are robust.
10

100 rpm

150 rpm

250 rpm

450 rpm

Figure 16. X-ray micro-computer tomography images of the PS/clay composites corresponding to the spectra shown in gure 12. The clay agglomerates attenuating the x-rays are mirrored by dark spots. The averaged radius of the agglomerates is well above 10 m.

Figure 17. Weight content of agglomerates wb (in percentage of clay net weight) as a function of A()/ A() at 450 nm for clay composites of PS, PA6 and PBT. The numbers adjacent to the symbols are the screw speeds in rpm. The solid line represents a t with a quadratic polynomial.

A()/ A() for different polymers as well as for quite different processing conditions seems to be surprising. A reasonable explanation for the former is the similar refractive index for all polymer melts which leads to similar scattering contrast. Furthermore, the normalization procedure following equation (3) seems to work rather well. Possibly, similar relations can be found for other (nano) llers which provide a relative simple and fast monitoring of particle dispersion using commercially available process spectrometers. It should be noted that the approach is limited to composites with a sufcient refractive index difference of the components. A similar approach was used before by Heller and Heller et al

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Figure 18. Simulated ultrasonic attenuation ( /f ) as a function of the frequency f for spherical particles immersed in a polypropylene melt. The particle diameters are indicated in the plot. For density and velocity of sound, typical values for chalk were used. The experimental frequency window (mainly restricted by the bandwidth of the ultrasonic transducers) is indicated by the shaded area.

Figure 20. Cross validation plot of the chemometric analysis of the spectra shown in gure 19.

Figure 19. Experimentally obtained ultrasonic attenuation ( ) as a function of the frequency for PP/chalk composites. The total amount of chalk was 40 wt%, while the ratio of coarse/ne chalk was varied.

sound scattering by the coarse chalk fraction. The attenuation spectra were evaluated by chemometric analysis using PLS. Figure 20 shows the cross validation plot. The correlation coefcient is 99%. It is therefore possible to use ultrasonic absorption spectroscopy for inline monitoring of agglomerates in composite melts with micron-sized llers. The application of ultrasonic attenuation spectroscopy for monitoring of the ller content has been shown elsewhere [47]. Ultrasonic measurements for the determination of ller dispersion during extrusion of PP/chalk composites are described in [31, 39] as well. In this work, the integral (not frequency-dependent) attenuation, sound velocity, melt pressure and temperature, throughput and chalk type were correlated with the degree of dispersion by a neural network. Since none of these parameters is so closely linked to particle size (and therefore ller dispersion) as the shape of the ultrasonic spectra, many more data sets to train the neural network are required compared to the number of ultrasonic attenuation spectra necessary to set up a chemometric model. 3.4. Morphology control by small-angle light scattering 3.4.1. State-of-the-art and experimental design. The characteristic domain size of the two-phase morphology in immiscible polymer blends to exhibit optimum mechanical properties (e.g. for impact modication) ranges from around 100 nm up to 1 m. This length scale can be probed by small-angle light scattering. Optimum coupling of the light to the sample can be achieved when measuring in the melt state. A rst setup for on-line light scattering experiments during extrusion based on a slit die with sapphire windows has been developed at NIST (National Institute of Standards and Technology, USA). Using this setup, the melt morphology of polyethlene/polystyrene blends [134, 135] and of liquid-crystalline polymer and polyethylene terephthalate blends [136] was studied. The NIST design allows a variation of the channel depth to adjust the sample thickness according to the scattering properties of the melt, in order to avoid multiple scattering. Light scattering experiments on polypropylene/polystyrene and blends of ethylene-butylacrylate copolymer with polyamide6 are described in [137]. Instead of using a slit die with
11

3.3.2. Ultrasonic experiments on micro composite melts. As an example, results on PP/chalk composites containing mixtures of two chalk types were compounded on a twin screw extruder (Coperion Werner & Peiderer ZSK-30). The PP was Moplen HP501H provided by LyondellBasell Industries. The rst chalk type was ne grained with an average diameter of 2 m (Omyalite 50H, Omya GmbH, Germany), while the second one was coarse grained with a mean diameter of 85 m (Omyacarb 130 AL, Omya GmbH, Germany). By mixing ne grained and coarse chalk types at a constant total ller content in the PP, a bimodal size distribution was created, which can be considered as a model system for a micro composite melt with agglomerates (coarse chalk). The total amount of chalk was kept constant at 40 wt%. The ultrasonic attenuation curves (pulse transmission technique, 4 mm sample thickness) of the composite melt at 190 C are shown in gure 19. For the melts containing mainly ne chalk, the attenuation increases monotonically with increasing frequency. A systematic shift of the spectra to lower frequency occurs with increasing amounts of coarse chalk, and at the high frequency limit, a maximum becomes apparent, which is related to the

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Figure 21. Scheme of a small-angle light scattering setup for morphology monitoring during extrusion.

Figure 22. Light scattering pattern (left column) and SEM images at different positions (see gure 23) within the extruded strand of a PP/POE blend for different throughputs (2.5 and 20 kg h1 ). The mixing ratio of PP to PEO was 75/25 wt%, the screw speed was set to 400 rpm and the barrel temperature was 230 C. The bar in the upper-left SEM image corresponds to 20 m and in the other images to 5 m.

sapphire windows, the melt ows through a central bore of a glass ball with a diameter of 10 mm. The diameter of the bore was 0.8 mm. This design was intended to also explore scattering in the wide-angle region. In [138], an experimental setup to monitor phase formation during blending in a mixer, based on detection of the back-scattered light, is described. It is assumed that monitoring of back scattering overcomes the problems with multiple scattering. Figure 21 shows schematically the design of a light scattering setup developed in our group [139, 140]. A temperature-controlled measurement slit die is attached to an extruder, and sapphire windows are mounted face to face at the melt channel so that the melt can be crossed by a laser beam. Typically, a heliumneon laser (wavelength: 632.8 nm) is used. The incident laser light is scattered by the phase domains in the melt, and the scattering cone is captured by a diffusive screen. The scattering pattern is projected onto the chip of a CCD camera. Alternatively, the diffusive screen can be replaced by a special lens system imaging the scattering pattern directly to the CCD chip, without an intermediate diffusive screen [141]. Due to geometrical restriction, an angular range between 1 and 30 can be detected.
12

3.4.2. In-line light scattering on polymer blends (example). In gure 22, the light scattering patterns and corresponding images from scanning electron microscopy (SEM) are shown for a blend of polypropylene (PP) with a polyolene elastomer (POE) for throughputs of 2.5 and 20 kg h1 . The mixing ratio of PP and PEO was 75/25 wt%, the screw speed was set to 400 rpm and the barrel temperature was 230 C. For PP Moplen HP501H from LyondellBasell Industries and for POE Exact 0201 from EXXON Mobil were used. At a throughput of 2.5 kg h1 , the scattering pattern (gure 22, rst image in top row) exhibits superposition of a pronounced needle and a circular pattern. This combined pattern mirrors the coexistence of elongated (needle) and globular domains (circular pattern) in the melt. Due to the ow prole in the slit die being perpendicular to the laser beam, the light scattering pattern is a superposition of morphologies resulting from different shear conditions. The corresponding morphologies are shown in SEM images (gure 22, top row) taken at different positions of the extruded melt strand. The analysed image plane and the positions of the SEM images are visualized in gure 23. Samples for the images were prepared by cold fracture at liquid nitrogen temperatures.

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Figure 23. Visualization of the plane within the melt strand analysed by SEM (left). The right image denes the positions where the samples for the SEM images in gure 22 were taken. In the right image, the parabolic ow prole and the domain types formed by different shear rates are schematically shown.

In the boundary and intermediate regions, elongated structures can clearly be seen in the SEM images, while in the centre the domains are globular. Such domain types are expected to be formed by a parabolic ow, which is sketched in gure 23 as well. At a throughput of 20 kg h1 , the scattering pattern (gure 22, rst image in the lower row) is almost circular with a faint reminiscence of the needle. This means that the domains are mainly globular. The SEM images support this. In the centre and the intermediate region only globular domains can be seen, while in the boundary region some faint needles are left. It is assumed that at the higher throughput (20 kg h1 in the described experiment), elongated structures are no longer stable. They are broken up by the increased shear forces leading to the formation of small droplets. Only in a boundary region, sticking to the wall some elongated structures remain. 3.4.3. Applications and limitations. As shown in the literature and in our experiments, small-angle light scattering can be used to monitor the morphology of polymer blends. The angular-resolved two-dimensional detection of the scattered light allows recognizing non-radial symmetrical scattering (see gure 22) from elongated blend structures. This is interesting for pilot-plant experiments on melt processing of blends as well as for monitoring purposes of production processes. In many cases, it is possible to extract information on domain size and shape from the scattering image. However, the refractive index of the blend components should not be much different. Otherwise, the blend will become turbid and multiple scattering will occur. For blends where the refractive index of the components differs greatly, light scattering can still be possible for very low contents of one of the components or at low sample thickness. Since the value of the refractive index is based on the chemical structure, similar refractive index values are obtained for chemically similar blend components. This is the case in PP/POE blends (the example shown here) or in blends of polystyrene with polycarbonate. 3.5. Monitoring of spots and gel particles Monitoring of spots, burners and gel particles can be done on extruded at lms (solid polymer) or in the melt. For the
13

detection of such particles, in crystallized or vitried materials, in-line imaging by commercial instruments and software is established. The running at lm is, for instance, lmed by a CCD camera and the images are immediately analysed by special pattern-recognition software. In cases where the polymer melt is not processed to a at lm, sometimes a at lm extrusion is installed in a bypass to monitor spots. The detection of spots via imaging of the melt was tested by Balke and Ing [142, 143]. The melt was pumped through a slit die equipped with windows and monitored in bright eld. Detecting gel particles was hardly possible, since the difference in refractive index is small. Another approach is the so-called micro-photometric method [144146], which is commercially available. Depending on conguration of the instrument, the transmitted and/or back-scattered light is measured in-line. The diameter of the scattering volume is 30 m. When the scattering volume is crossed by a particle, the transmitted light is reduced and/or the intensity in the back-scattering detector increases. The small scattering volume was chosen to suppress multiple scattering in the case of higher particle concentration. We have recently applied our small-angle light scattering setup in combination with the ultrasonic transmission technique described in sections 3.3 and 3.4 for in-line detection of spots and gel particles. Figure 24 shows the uctuations of the scattered light intensity (left) and the amplitude of the ultrasonic attenuation (right) as a function of the processing time for a thermoplastic elastomer melt during extrusion. For the scattered light the circularly integrated scattering intensity for a scatting angle of 3 was taken. At process time zero, a small amount of material containing spots (diameter about 0.7 mm) was added. After the residence time, the melt with the spots arrives at the respective detectors. This is indicated by the vertical lines in gure 24. The slight difference in time is due to the different positions of ultrasonic and light scattering detection along the melt stream. The short spikes in the scattered light intensity and ultrasonic absorption indicate particles with higher optical or acoustical scattering contrast in the initially optical clear melt. On comparison of the right and left graphs in gure 24, good correlation between light and ultrasonic scattering events is indicated. It is obvious that ultrasound detects a larger number of such events, which can be explained by the larger scattering

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Figure 24. Fluctuations of the scattered light intensity (left) and the ultrasonic attenuation of the transmitted signal (right) as a function of the processing time for a thermoplastic elastomer during extrusion at 190 C.

volume for sound transmission (8 mm diameter transducers) compared to light scattering (diameter about 4 mm of the laser beam). Both methods, ultrasonic measurements and light scattering, are sensitive to spots. In other experiments, we found that ultrasonic spectroscopy is able to detect gel particles as well. This can be explained by the different origin for scattering contrast: refractive index for light scattering and density and/or modulus difference for ultrasound. Since the ultrasonic pulse transmission technique is not limited to optical transparent samples and due to the lower price of the setup, the method is expected to have a high potential for detection of spots, burners and gel particles in polymer melts.

4. Concluding remarks
The aim of this report was to review the state-of-the-art of in-line, on-line and at-line process monitoring during polymer melt processing. In addition to optical spectroscopy, usually applied for monitoring chemical composition or reactions (e.g. for reactive extrusion), we concentrated on morphology monitoring by scattering methods using electromagnetic or ultrasonic waves. Examples for the application of angledependent scattering and frequency or wavelength-dependent transmission experiments are given. The sensitivity for a given composite or a blend was found to depend on the ratio of the wavelength to the main domain or particle size as well as the scattering contrast. The optical methods are sensitive to particles in the range of hundreds of nanometres, whereas ultrasonic absorption measurements are useful for micro composites. The latter can also be used for turbid samples. In addition to morphology control, light and sound scattering can be applied to detection of spots, burners or gel particles. The detection of uctuations of the measured properties can be as well used for monitoring of the process stability, e.g. along the screw of an extruder [32, 34]. In addition to optical and acoustic spectroscopy, x-rays using synchrotron sources or terahertz scattering have been used for morphology control. Although these methods provide interesting information, they are still limited to pilot plants or basic experiments and were not considered here. The same is true for in-line solid-state NMR, where the problems for high-temperature applications are not yet solved.
14

In addition to chemical and morphology control, inline measurements of macroscopic properties were discussed. Examples for monitoring of electrical conductivity during extrusion and injection moulding are given for conductive nanocomposites. In summary, one can state that a huge number of experimental methods have been adapted, modied and tested in the last two decades for in-line or on-line monitoring of polymer melt processing. Although all this knowledge and an increasing number of process probes and commercial setups are available, the implementation of in-line control for polymer melt processing was slower than expected at the beginning of this development. This is mainly due to the low added value of plastics products and the dominance of small- and medium-sized companies with frequently changing products. Another reason is the need for specic qualied personnel. However, industrial application of extrusion monitoring for pharmaceutical products or high price polymers (e.g. melt glues) is known. Based on the accumulated knowledge and the commercially available instrumentation, the breakthrough predicted by road maps on process control can be expected in the next few years. For polymer processing, much work has been done on extrusion monitoring of thermoplastics. Since the nal property of the product appears in the solid state (glassy or semi-crystalline) of the polymer, there is an increasing need for in-line monitoring during injection moulding or at lm extrusion. The same is the case for monitoring of process stability along the production line in order to guarantee constant quality and processing reliability. Besides the thermoplastics considered in this report, thermosets are another important class of polymeric materials with actually growing importance, for example as matrices for bre composites in aerospace applications. There is also an increasing need for in-line monitoring of thermoset processing. Monitoring of curing reaction is described in [147150] and references therein. For instance, in-line DRS was actually applied for in situ monitoring of morphology changes during curing of thermoset/thermoplastic blends [148, 150]. The microstructural evolution and the development of internal stress of an epoxy system were observed in situ by DRS, ultrasonic and refractive index measurements [149]. Solution

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[151] and bulk polymerization [152]which are analogous to thermoset curingwere monitored successfully via in-line DRS as well.

Acknowledgments
Part of the presented work was funded by the Bundesministerium f ur Wirtschaft und Arbeit via the Arbeitsgemeinschaft industrieller Forschungsgesellschaften (AiF Project Nos. 10943, 11961, 73Z, 122Z, 190 ZBG, 14452N, 14359N, 14454N, 15098N, 15988N and 16256N). Further part was funded by the German Federal Ministry of Education and Research (BMBF) within the framework concept Research for Tomorrows Production (project no 02PU2394 and 02PU2361). We would like to thank Torsten Finnberg for carefully revising the manuscript. We thank G unter Vulpius, Harald D orr, Norbert Schuchmann and Shilpa Khare (DKI Darmstadt) for their help in performing the extrusion and injection moulding experiments. We also thank Dr Dieter Fischer (Leibniz-Institut f ur Polymerforschung Dresden eV), Dr Petra P otschke (LeibnizInstitut f ur Polymerforschung Dresden eV), Dr Hans Kothe, Felix Simon, Alexander Ohneiser, Martin Engel, Sergej Dudkin, Kai Wassum, Dr Yong Wang, Dr Yaming Wang and Dr Donghua Xu (DKI Darmstadt) for their valuable experimental contributions and helpful discussions. Finally, we would like to thank all our industrial partners, in particular Kathrin Lehmann (Evonik Goldschmidt GmbH), Dr Dieter Lilge (LyondellBasell Industries), Dr Richard Lamour (Bayer AG), J urgen Ramthun (Bayer AG), Dr Michael Bierdel (Bayer Technology Services GmbH), Dr Reiner Rudolf (Bayer Technology Services GmbH), Dr Helmut Meyer (Bayer Material Sciences GmbH), Professor Christian Kohlert (Kl ockner Pentaplast), Peter Lehnhoff (Brabender GmbH & Co. KG), Uwe Kirschner (Sentronic GmbH) and Steffen Piecha (tec5 AG).

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