Applied Rheology

Sp Anton Paar Applied Rheology With Joe Flow on Rheology Road Thomas G. MezgerThomas G. Mezger Applied Rheology With Joe Flow on Rheology Road Anton Paar GmbHCopyright © 2014 Anton Paar GmbH, Austria. ISBN 978-3-9504016-0-8 All rights reserved, in particular the right of reproduction, distribution and translation. No part of this book is allowed to be reproduced in any form whatsoever (photocopy, microfilm or by any means) without the written consent of the publishing company nor may it be stored, processed, reproduced or distributed using electronic systems. Published by Anton Paar GmbH. Printed in India. Anton Paar GmbH Anton-Paar-Str. 20 8054 Graz, Austria Tel: +43.916 257-0 Fax: +43 316 257-257 Email: info@[Link] Web: [Link] 1st edition January 2015 Layout: Werbeagentur Rypka GmbH, 8143 Dobl/Graz, [Link] Subject to change without notice | XRRIAOO1EN-BContents Introduction 1. Rheology and viscous behavior sacl 2. Simple methods for measuring viscosity... cence 3. Rotational viscometers, oscillatory rheometers and measuring systems... 4. Definition of terms: Shear stress, shear rate, law of viscosity, kinematic viscosity..........0sesssesrse seven §. Rotational tests, introduction cessiee 27 6. Flow behavior, flow curve and viscosity curve... 7. Yield point, evaluation using the flow curve . 8. Other flow curves and viscosity curves 53 9. Time-dependent flow behavior (rotation) 59 10. Temperature-dependent flow behavior (rotation)1. 12. 13. 14, 15. 16, 17. 18. 20. a, 22. Viscoelastic behavior............ Definition of terms: Shear strain or shear deformation, shear modulus, law of elasticity .............ses cscs oe BT Yield point, evaluation using the deformation/shear stress diagram...... Oscillatory tests... Amplitude sweeps... oes 401 Frequency sweeps Time-dependent behavior (oscillation)... ses 23 Temperature-dependent behavior (oscillation)...... see 7 Torsional tests on solid samples...... 1149 Tensile tests on polymer melts, films and foils .........0.0.0 153 Tips for avoiding measuring errors ... The end of the stroll along Rheology Road ........cs.:sceineel 77 Appendix: Symbols, signs, abbreviations, units, references, standards. Taare AME ING OX oecsccsesseseseseetcseseseessneee o - seeseee BFIntroduction Introduction and starting point for the stroll along Rheology Road deforms roll, honey, 1 their pl you can line th odu a the liquids, on the far right the solids, lassification and de expert in the fields of rhec Rheology 0 be and as: deformation and flow behavior of materials. Rheometry is the term for everythir he measurement of rheological gh the wor8 ee Anton Paar Imagine that you were to build a small house over each of the substances mentioned above. After this you could take a stroll along the row of houses just as you would on any street, Let us calll this street that only exists in our imagination Rheology Road. Between the beginning and the end of this road there are liquids with viscous behavior at one end and solids with elastic behavior at the other. Or, in rheological terms: On the left side, there are fluids that have an ideally viscous behavior, for example water and oil (see Chapter 6). The cube on the far right side is a symbol for the deformation behavior of ideally elastic materials, which are very rigid and stiff, such as stones and steel (Chapter 14). in between, there are substances that act in a viscoelastic way, showing a mixture of viscous and elastic properties. The substances on the left side of the road are the viscoelastic fluids (Chapters 4 to 17, 14 to 18, 20). The key property of these substances is that they are in a liquid state. However, when they are subjected to a rapid and large deformation, they can be prone to roping. In this event they show some elastic behavior. Examples are shampoo, glues and dough. On the right side of the road there are the viscoelastic solids (Chapters 11 to 20). At rest they show a rigid consistency. However, when a sufficiently large force is applied, some of these materials can be easily deformed. If the deformation force is very high, the substances wil finally, more or less, start to flow or break in a brittle way. Examples of such substances include lotions, creams, toothpaste, gels and soft erasers. Figure 0.3: This is @ map of Rheology Road. t stretches ‘from the "District of Liquids’ on the left with fluids displaying a viscous flow behavior to the “District of Solids” on the right where the materials have an elastic deformation behavior. Joe Flow is pleased that you selected him to be your guide an the stroll along Rheology Road. He would like to provide helpful information for all users of rotational and oscillatory rheometers in order to make measurements useful, no matter what type of sample is to be tested. The stroll along Rheology Road in this book starts on the left side at the “District of Liquids" and ends on the right side at the “District of Solids” (Figure 0.3). To facilitate this discovery tour, all signs and symbols, abbreviations, Greek characters, units and standards are listed in the Appendix, which also features a comprehensive ‘subject index. In the list of references you will find text books (for example (3), [6] and /8)) and e-learning CDs [1] that provide in-depth information on the subject for the interested user.1. Rheology and viscous behavior Rheology is a branch of physics. Rheologists describe the deformation and flow behavior of any kind of material. The term originates from the Greek word “rhei” meaning “to flow” (Figure 7.1). Rheometry is the measuring technology used to determine rheo- logical properties. What is viscosity? All iquids are composed of molecules; dispersions also contain some significantly larger particles. When put into motion, molecules and particles are forced to slide along each other. They develop a flow resistance caused by internal friction: Larger components present in a fluid are the reason for higher viscosity values. Why is that so? Molecules in fluids come in different sizes: solvent molecules approx. 0.5 nm, polymers approx. 50 nm coiled ball diameter at rest) and mineral particles approx. 5 rm = 5000 nm, One nanometer (1 nm) equals 10° m; one micrometer (1 jum) is equal to 10° m, This means that the size ratio between molecules and particles is in the range from 1:100 to 4:10,000 2)0 Regpnanirie ‘The ratio of 1:1000 can be illustrated with the following Figure: The molecules are fish, each of them 10 cm (0.1 m) long, while the particles are ships with a length of 100 m (Figure 1.3). Z 6 6 » i Figure 1.2: Comparison of sizes: solvent molecules 5 (Gots), polymer molecules (smal circles) and particles (red ® outline). Viscosity isthe intemal tition that occurs when all components in a flowing kquid are forced to slide along each other a : = é| ——_— Figure 1.3: Visualization of the size ratio of 1:1000, which is similar to the size ratio of molecules and’ particles in a fluid. It can be compared with the size difference between smal fish and large ships.2. Simple methods for measuring viscosity If you want to describe the flow behavior and deformation of matter in everyday language, you will probably use terms such as thick and thin, soft and solid. a) Spatula test The sample to be tested is scooped up with a spatula; the spatula is then held in a horizontal position or slightly titted while pointing down. This very simple test shows that a thick, highly viscous, non-flowable paste will stick to the spatula for a prolonged time without dripping, whereas a thinner, low-viscosity ion will run off quite quickly due to its own weight (Figure 2.1) b) Finger test This test is used to feel the firmness, stiffness, brittleness, stickiness or tack of pastes, adhesives, printing inks, lubricating grease, bitumen or dot Long” behavior means that the sample is prone to stringiness, while behavior means a brittle fracture without stringiness (F eaniaeie cet _—— 4 T Gey TT D w L yo42 How does the material break? Into crumbs? As a cream or similar to butter? With long or short fibers? c) Flow cups Flow cups are used for simple quality-control purposes of low-viscosity liquids. The parameter measured is the flow time that a defined amount of liquid needs to flow ‘through an orifice at the bottom of the cup (Figures 2.3 and 2.4). The shorter the flow time, the lower the viscosity of the sample. This measurement is based on gravitational force. Therefore, please note that the viscosity data obtained with this method is always dependent on the weight or density of the sample. Flow cups come in a variety of geometries, Most common are ISO cups, Ford cups and DIN cups according to ISO 2431, ASTM 01200 and DIN 53211 (withdrawn), (Figure 2.5). Please note that, with different types of flow cups, the same flow time does not necessarily mean that the viscosity is also the same. Typical samples for such a test include mineral olls, solvent-based coatings, low-viscosity gravure and flexo printing inks. Flow cups will only deliver meaningful viscosity values for liquids with ideally viscous fiow behavior (see Chapter 6.1). © by Anton Poor GmbH hed | | | | Figure 2.3: Flow cup for the determination | ofa sample's viscosity: After | opening the orifice, the flow time oe _| is determined 1). 4) Falling-ball viscometers and micro falling-ball viscometers These instruments are used to define the time a ball needs to sink or roll down over a defined distance through a liquid sample contained in a glass tube supported by gravitational force only (according to ISO 12058 and DIN 83015). To enable the visual evaluation, the sample should be transparent. The parameter measured is the viscosity, dependent on the weight or density of the sample. If opaque samples are to be measured, it is possible to track the falling ball by means of induction in an electro-magnetic field. Specific designs are micro falling-ball visco- meters that are used for the smallest sample quantities such as biological fluids, protein‘Simple methods for measuring viscosity 13 Figure 2.4 (left) Flow cup measurement: The shorter the flow time, the lower the viscosity of the liquid sample. Figure 2.5 below Types of flow cups: The orifice in ISO cups (lef) is longer than in DIN cups and Ford cups (right) (7). solutions, dilute polymer solutions, low-viscosity inks and beer wort. Please note: Falling- ball viscometers, where the angle of the tube cannot be adjusted, will deliver meaningful viscosity values only for liquids with ideally viscous flow behavior (see Chapter 6.1). €) Glass capillary viscometers Using these devices, the viscosity is determined by measuring the time a defined amount of liquid needs for travelling through a capillary with a defined geometry. The parameter measured is the viscosity dependent on the weight or density of the sample. ‘Typical samples for this type of measurement include mineral oils and dilute polymer solutions. Please note: Glass capillary viscometers will deliver meaningful viscosity values only for liquids with ideally viscous flow behavior (see Chapter 6.1). f) Rotational tests with spindles Using a rotational viscometer, the rotational speed of a spindle is preset after inserting the spindle into the cup containing the sample. This device measures the torque that arises from the flow resistance of the sample. Spindles are available in various geometries, including cylinders, disks, pins and cross-shaped T-bars (Figure 2.6). In most cases, the viscosity values stated are relative values and not absolute values. The difference is that absolute values are not correlated to the size of the measuring system, whereas relative values are (see Chapter 3.1). For the determination of absolute values, certain contitions for standard geometries must be complied with; for example, @ narrow measuring gap that provides for consistent shear conditons. This does not apply to the spindles mentioned above and therefore they are called relative measuring systems. These kinds of spindles should be used for very simple quality control tests only. Chapter 2 (© by Aten Paar GmbH14 I rT Figure 2.6: Typical spindle geometries of relative measuring systems, from the left: cylinder, disks, pins, hollow cylinder and a T-bar g) Rotational tests with other relative measuring systems Many industries use a wealth of other measuring geometries for the determination of relative viscosity values; for example, helical stirrers and stirrers with perforated blades for dispersions containing large particles (such as sand in building materials), stirrers with inclined blades that prevent setting of particles in dispersions (e.g. starch particles prior to gelling), paddle stirrers, anchor-shaped rotors, rotating devices with vanes or laterally protruding pins, paddles (such as the so-called Krebs spindles for paints, measuring the viscosity in Krebs Units or KU) as wel as ball measuring systems (eg. for building materials and particulate food systems with large-particles (up to 10 mm) such as fruit pieces in jam or meat particles in pasta sauce), see Figure 2.7 T Figure 2.7: Relative measuring ‘syStems or stivers: helically shaped, with perforated or incined blades, anchor shaped, as rotors with vanes or pins, as @ paddle system such as the Krebs spindle for coatings, or as a ball measuring system [8]. Please note: The viscosity values determined with relative measuring systems are always dependent on the spindle used. Therefore, values obtained with different spindles cannot be compared with each other. In this case, it would make sense to only present raw data preset and measured by a rotational viscometer .., the rotational speed and torque.3. Rotational viscometers, oscillatory rheometers and measuring systems Modern rheometers can be used for shear tests and torsional tests. They operate with continuous rotation and rotational oscillation (Figure 3.1). Specific measuring systems can be used to carry out uniaxial tensile tests either in one direction of motion or as oscillatory tests. » KRae Px Anton Paar Detailing the terms viscometer and rheometer: with a viscometer, the viscosity can only be determined via rotational tests, mostly speed-controlled, and presented as flow curves or viscosity curves. Rheometers are able to determine many more rheological parameters. 3.1 Absolute measuring systems for rheometers Absolute values, for example viscosity, can only be determined with absolute measuring ‘systems. In contrast to relative values, absolute values do not correlate with the size of the measuring system. They have a relatively narrow shear gap as defined by specific standards for measuring systems such as ISO 3219 and DIN 53019. These standards describe the following measuring system geometries: cone/plate, concentric cylinders and plate/plate (Figure 3.2). Figure 8.2: Measuring systems: ‘Cone/plate (with radius R, cone angle o, truncation 2); Plate/plate (with radius R, distance between plates H); and concentric eyinders (vith bob rads A and up radius R, and internal angle a at the tp of the bob) a) Cone/plate (CP) or cone-and-plate measuring systems CP systems are suitable for all types of fluids; however, their applicability to dispersions is limited to a certain maximum particle size. Such systems are described in the measuring system standards ISO 3219 and DIN 53019. According to the ISO standard, it is recommended that a cone angle of o: = 1° is used; cones with an angle of more than 4° are considered to be sub-standard, For precise measurements, CP systems with truncated cone tips are the systems of choice. The decisive parameter is the measure, a, of the gap set at the center of the cone. The rule of thumb for the maximal acceptable particle size, d, is: d < (@/10). Example: For a CP 25-1 (with a diameter of 25 mm, cone angle = 1°), the dimension of the truncation or gap setting for the measuring position is typically a = 50 um. This means that the maximal acceptable particle size would be approximately 5 um.Rotational viscometers, oscilatory rheometers and measuring systems 47 Figure 3.3: Filing of a cone/plate measuring system after gap setting: a) overfled, b) undertiled, c) corract amount (according to DIN 51810-1) It is important to load a CP system with the correct sample quantity (Figure 3.3). Trimming the sample: To trim means to cut or adjust, to prune, shave or proportionate something correctly. Place the sample (use slightly more than actually needed) at the center of the lower plate. First, reduce the gap to the trim gap position. For CP systems, this is the width of the measuring gap plus for example an additional 10 um. Make sure that the gap of the measuring system is completely filed with the sample. Use a trimming tool (e.g. 2 spatula) to strip off any excess material along the brim of the plate so that the sample corresponds to the external diameter of the upper plate. Make sure that no sample material is removed from the measuring gap. Next, the final measuring gap width is approached. Due to slight overfiling, the sample will then form a small bulge at the edge. Advantages of CP systems: There are uniform shear conditions in the entire conical gap. Only a small amount of the sample is required, which allows for quick temperature adjustment as well as for easy cleaning (Example: The sample volume required for a CP 25-1 is less than 0.1 m). Disadvantages of CP systems: Due to the narrow gap in the center, dispersions can only be tested up to a certain maximum particle size. At the edge of the cone, effects such as sample migration out of the gap or skin formation (drying of the sample) might occur. Special accessories: To prevent evaporation of solvents, a special hood or a solvent trap can be used b) Concentric cylinder (CC) measuring systems Concentric cylinder systems are commonly used for tests on low-viscosity liquids. Such systems are specified in the measuring system standards ISO 3219 and DIN 53019. To ensure a relatively narrow measuring gap, the ratio of the radii of cup and bob must not exceed 1.0847. Example: In a CC 17, the diameter of the bob is 17.0 mm, thus the diameter of the cup should be 18.44 mm (= 1.0847 x 17 mm). This means that the gap has a width of only 0.72 mm (18.44 - 17.0 mm = 1.44 : 2) Chanter 3‘2 ee Advantages of CC systems: The cup is easy to fill; there is a filing level mark inside the cup. Due to the large outer surface of the cup, the temperature of the sample can be easily controlled from the outside. Fluids with low surface tension cannot flow out of the cup (as may happen with CP or PP systems) J [ (by Arion Paar GmbH Disadvantages of CC systems: as A relatively large amount of sample is required. This results in a longer temperature-equilibration time and more cleaning effort. Figure 8.4: Cross-section of a profiled cytindrical bob, used for . samples that tend to have wall-siip Special accessories: affects To prevent evaporation of solvents, a special hood or a solvent trap can be used. CC systems with a sandblasted or profiled surface might be used to prevent wall-slip effects (Figure 3.4). The surface profile depth is 0.56 mm, for example. Typical applications for these systems are granular pastes or dispersions used as bullding materials. Disposable cups and bobs are available for hard to clean samples for single use. ©) Plate/plate or parallel plates (PP) measuring systems PP systems are recommended for testing pastes, gels, soft solids or highly viscous polymer melts. Such systems are described in the measuring system standards ISO 6721-10 and DIN 53019. Recommended gap widths are from 0.5 to 1.0 mm. Example: PP 25 means that the movable plate has a diameter of 25 mm. Trimming the sample: In general, the same principles apply for filing the sample into PP systems as for CP systems. Here, however, a larger trim-gap position is actually used for trimming; for example 25 um; or even O um when testing bitumen (asphalt binder). Advantages of PP systems: Arelatively small amount of sample is required. Due to the adjustable gap, variable measuring conditions can be set. It is also possible to test highly viscous samples {including polymer metts, uncrosslinked silicone], dispersions with larger particles, gels (with three-dimensional superstructure) and soft solids (such as cheese and elastomers). Cleaning is quick and easy. Disadvantages of PP systems: There are no constant shear conditions in the gap because the shear rate at the edge of the plate is higher than at the center of the plate. At the edge of the plate, effects such as sample migration out of the gap or skin formation (drying of the sample) might occur.(© by Aoton Paar Orbit Rotational viscometers, osciatory theometers and measuring systems 19 Due to the relatively large gap width, there might not be a uniform sample temperature if the temperature is controlled from one side only or if the temperature-equilibration time is too short. Special accessories To prevent evaporation of solvents, a special hood or a solvent trap can be used. PP systems with sandblasted or profiled surfaces are available in order to prevent wall-slip effects. Typical applications include oil- and fat-containing samples from the food, cosmetics, pharmaceutical and medical fields. For samples with curing, or which are difficult to clean, there are disposable PP systems available consisting of a disposable plate and a disposable dish for single use (Figure 3.5). Typical applications are reaction resins and powder coatings. b @ ee) Figure 3.5: Exploded view of a disposable-plate measuring system with shaft (1), disposable plate @), dlsposabie alsh (9) and alsh holder (4) which is ‘mounted to the bottom temperature control plate of ihe rheometer (9). Chapter 3 Figure 3.6: Double-gap measuring system with the four radii RT to Fé resulting from the shape of the cup showing the geometry of a circular gap, from the holow cylinder bob, as well as from the length L of the immersed part of the bob (© by Anton Paar Gmbit4) Double-gap measuring systems (DG) According to DIN 54453, DG systems have a special geometry that provides for a large contact area between the sample and the surface of the DG system (Figure 3.6). These systems enable testing at high torque resolution, and are used in particular for testing low-viscosity liquids such as water. 3.2 Ball bearings and air bearings for rheometers Every drive needs a bearing; this also applies to the motor of a rheometer. However, mechanical bearings such as ball bearings show a certain bearing friction that should Not be neglected, as it may affect the precision of rheometrical measurements. Ina ball bearing, for example, the balls in the pathway roll between the stator (static outer ring) and the rotor (rotating inner ring), which is connected to the rotating shaft of the rheometer. Such a bearing generates a certain amount of rolling friction in the form of a braking torque. This may result in incorrect measuring results, in particular in the lower rotational speed and torque ranges, For testing low-viscosity fluids, such as water, at low torques with the highest precision, users prefer advanced rheometers equipped with air bearings. With these instruments, there is only compressed air present in the gap between the rotor and the stator of the drive. This means that a compressed-air connection is required for the operation of the rheometer.The Two-Plates Model is used to define the rheological parameters needed for a scientific description of flow behavior (Figu 42). Shear is applied to a sample sandwiched between the two plates. The lower stationary plate is mounted on a very rigid support, and the upper plate can be moved parallel to the lower plate Before calculating the viscosity, it is necessary to first define the shear stress and the shear rate. d to the sample while the lowe(© by Amon Paar Gmbh 22 > Anton Paar Figure 4.2: Calculation of shear stress and shear rate using the Two-Plates Model with | shear area A, gap width h, shear force F and velocity v a) Shear stress Definition: t = F/A with shear stress t (pronounced: tau), shear force F (in N, newton) and shear area A (in m?), see Figures 4.3 and 4.4. ‘The unit for shear stress is 1 N/m‘ 1 Pa (pascal). The shear stress is calculated by the software. The following data are required for the calculation: A rheometer records the shear force via the torque at each measuring point. The torque is either preset or, if the rotational speed is the preset value, it is determined via the flow resistance force of the sample. The size of the shear area is also known for the measuring system used. Figure 4.3: Two-Plates Mode! used to define the ‘Figure 4.4: Shear stress tis defined ‘shear stress using the parameters shear force F as shear force F divided by shear and shear area A of the upper, movable plate area A, b) Shear rate Definition: y= v/h with shear rate ¥ (pronounced: gamma dot), velocity v (in rr/s) and shear gap h (in m), see Figures 4.5 and 4.6. ‘The unit for shear rate is 1/s = 1 s", also called reciprocal seconds. The shear rate is calculated by the software. The following data are required for the calculation: A rheometer records the velocity as the rotational speed at each measuringDefinition of terms: Shear stress, shear rate, law of viscosity, kinematic viscosity 23 Figure 4.5: Two-Plates Model used to define the ‘Figure 4.6: The shear rate is defined shear rate using the parameters velocity, v, of the as the flow velocity, v, divided by the upper, moveable plate and distance, h, between shear gap width, A the plates point. The rotational speed is either preset or, if the shear force is the preset value, it is determined via the flow velocity of the sample. The size of the shear gap is also known for the measuring system used. Sometimes the following terms are used as synonyms for shear rate: strain rate, deformation rate, shear gradient. Practical applications and the corresponding typical shear rates: 1) Low-shear range is the range with very low shear rates or even shear conditions very close to the state at rest. This includes all shear rates below 1 s" Examples: sedimentation of dispersions at between 0.001 and 0.01 s*; levelling of coatings at between 0.01 and 0.1 s*; sagging of coatings at between 0.01 and 1 s" (Figure 4.7) 2) Medium-shear and high-shear ranges include all shear rates above 1 s” Examples: - Dip coating from 1 to 100 s* - Extrusion from 10 to 1000 s* - Pipe flow, pumping, filling, mixing, stirring processes from 10 to 10,000 s* - Painting, brushing from 100 to 10,000 s* Figure 4.7: The leveling and sagging behavior of a ~ Spraying from 1000 to 10,000 s* coating aiter application with a brush is an example “digi: i of very low shear rates. Will any brush marks remain High-speed blade coating om ‘on the paint surface or wil the surface turn out to be 100,000 to 1,000,000 s* Shiny and glossy? Chait 4(by Anton Paar GmbH 24 en Figure 4.8: Application of paint Figure 4.9: Squeezing toothpaste out of a tube: Demonstration for calculating with a brush: Demonstration for the shear rate based on discharged volume, flow time and radlus ofthe tube’s calculating the shear rate based nozzle on the application velocity and the thickness of the wet paint layer Examples for the calculation of shear rates a) Painting with a brush (Figure 4.8) Calculation of the shear rate using the Two-Plates Model and the following definition: yev/h With a painting speed of v = 0.5 m/s and a thickness of the wet layer of h = 200 pm = 0.2 mm = 0.0002 m, the resulting shear rate is 2500 s b) Flow of toothpaste out of a tube (Figure 4.9) The shear rate of flow in capillaries, tubes and pipes is calculated using the Hagen/Poiseuille formula: Y=(4-W/ (a RPA) With a discharged volume of V = 1 cm? and a flow time of t = 1 s, the volume flow rate is VA = 10* m*/s. Based on a tube outlet with a diameter d = 6 mm or radius and circle constant m = 3.14, the shear rate is: Y= (4- 10° m/s) / (n - 27 + 10° m’) = 47.2 s* = approx. 50s" Figure 4.17: The Law of Viscosity,© by Anton Paar OreH Definition of terms: Shear stress, shear rate, law of viscosity, kinematic viscosity ©) Viscosity or shear viscosity Definition: n = Anton Paar a) Raw data and rheological parameters for rotational tests Its a disadvantage that the physical values determined as raw data by the rheometer are correlated to the size of the measuring system used. In contrast, the rheological parameters shear stress and shear rate are independent of the selected measuring system. They are the basis for determining the viscosity. Both modes of operation, controlled shear rate, CSR or CR, and controlled shear stress, CSS or CS, are explained in Tables 2 and 3. The following applies: Torque M is in newton meter, Nm, where 1 Nm = 1000 mNm (mill-newton meter) = 10° LNm (micro-Nm); rotational speed n in min’ meaning revolutions per minute (pr). eruka oo controlled shear rate (CSR) _ test parameters Raw data ftom the rheometer Rotational speed n fn min) | Torque M tin Nm) | Rheological parameters, calculated | Shear rate ‘(in 6) Shear stross tin Pa) Table 2: Rotational tests with controlled shear rate (CSR), raw data and sheological parameters ean eens controlled shear stress (CSS) _ test parameters Raw data from the rheometer Torque M (in Nev Rotational speed n (n min") | Rheological parameters, calculated —_| Shear stress € (hn Pa) Shear rate (ins) Table 3: Rotational tests with controlled shear stress (CSS), raw data and rheological parameters For calculating the viscosity as n = 1/7, the type of operation mode is irrelevant because the parameters shear stress and shear rate are both available, either as a preset value or as a result of the test. For converting raw data into rheological parameters, there are two conversion factors available: one is used to convert the torque into the shear stress, the other for converting the rotational speed into the shear rate. They must be known for each measuring system; this is why the supplier always provides a data sheet for each individual measuring system. Additionally, they are also stored in the corresponding software program.Rotational tests, introduction 29 b) CSR and GSS preset profiles for flow curves (Figure 5.3): 1) Preset rotational speed or shear-rate ramp, usually ascending or descending in steps 2) Preset torque or shear-stress ramp, usually ascending or descending in steps For shear rates above 1 s", a typical setting recommended for both modes is a duration of at least 1 to 2 seconds, which is to be maintained for each measuring point because the sample needs a certain time to adapt itself to each shear step. Figure 5.3: Preset profiles for flow curves as time-dependent step-like ramps, here with 15 steps: corresponding to 15 measuring points, with controlled shear rate CSR (left) and controlled shear stress CSS font) Chapter 5Sp ‘Anton Paar6. Flow behavior, flow curve and viscosity curve Viscosity values are not constant values as they are affected by many conditions. You probably have already had experience in your own kitchen of salad oil, yoghurt or a highly concentrated starch suspension flowing in very different ways when stirred in a bowl or mixed with other food, The subject of this chapter is flow behavior under shear at constant temperature, Flow behavior can be presented in two types of diagrams (Figure 6.1, a) Flow curves with shear stress t and shear rate 7, usually with the latter plotted on the x-axis b) Viscosity curves with Th, viscosity 1 and shear rate 7 (or shear stress 1), usually Ta with the latter plotted on the t : =~ x-axis. Applying the Law of Viscosity, each measuring point is lowsse Biv werven The advantage of diagrams on a logarithmic scale is that a range of very small values can be illustrated clearly on the same diagram as much larger values. This is not possible with a linear scale, Often the biggest changes in viscosity just take place within the range of low shear rates, which is below y= 1s". With a presentation on a linear ‘scale, however, this range can only be depicted to a limited extent. 5 = é & & | 6 6.1 Ideally viscous flow behavior The terms ideally viscous and Newtonian flow behavior are synonyms (Figure 6.2). Typical materials from this group include water, mineral oil, slicone oil, salad oil, solvents such as acetone, as well as viscosity standards (e.g, calibration oils). E80 wo | | 4g 1000 | BL mPas Pa} | Pas ba pl ® 60 reeevveveseveerrerrgetoerrry| £) 0) tr eeemernemrst 10 ly © o, on + gt! | 20 so) foe ot | 20 20 | } 0 10 oor | | a 0 1 | 0 200 400 600 s" 1000 || 9oa1 eer or 10, 100 1 | | ‘oy | — a —— I Figure 6.3: Flow curve and viscosity curve of a Figure 6.4: Flow curve and viscosty curve of ‘mineral oll, presented on a linear scale. Across the _an iaealy viscous sficane oll, presented on a entire measuring range, the viscosity of the mineral logarithmic scale for better iltustration of the values il ramains constant, thus showing ideally viscous _in the low shear range. ow behavior,Flow behavior, flow curve and viscosity curve 33 What is the viscosity value of water at ambient temperature? This is an interesting question and not just for wand recora’sivimrriers Figure 6.5: With Joe Flow at the swimming poo! Measuring example: Flow curve and viscosity curve of a mineral oil (Figure 6.3). ‘A mineral oil was tested using a cylinder system at a temperature of T = +50 °C, The shear-rate-controlled test was carried out with 30 measuring points in a step-like ascending arrangement. Total measuring time was t = 180 s; this corresponds to 6 s for each measuring point. The evaluation shows that the viscosity remains constant across the entire measuring range. Thus the oil displays ideally viscous behavior. Measuring example: Flow curve and viscosity curve of a silicone oil (Figure 6.4) Asilicone oil was tested in a cone/plate system at a temperature of T = +23 °C. A shear-rate-controlled test was carried out using ascending logarithmic steps. The uration for each measuring point was decreased continuously with increasing shear rates, starting at a shear rate of 0.001 s with 1000 s for each measuring point and ending at a shear rate of 1000 s* with only 1 s for each measuring point. The evaluation shows that the viscosity remains constant over the entire measuring range, even at very low shear rates. Thus the silicone oil displays ideally viscous behavior. A diagram on a logarithmic scale was chosen for the presentation, which allows the values even at low shear rates to be displayed very clearly. Measuring example: Flow curve and viscosity curve of water (Figures 6.5 and 6.6) Water was tested in a double-gap system at a temperature of T = +20 °C. ‘A shear-rate-controlled test was carried out using ascending logarithmic steps. ‘© by Anton Paar Gmbit© by Anton Paar Grit 34 As expected, the water showed a constant viscosity of n = 1 mPas, which is ideally viscous behavior. ‘The presentation in the diagram was limited to a shear-rate range of between 0.2 and 200 s*. At lower shear rates, the detectable torque signal would be too small under these measuring conditions. At higher shear rates, turbulent- flow effects in the gap would cause disturbances to the flow. There is no way of preventing such effects when testing fast-flowing low-viscosity liquids. In this case, the requirements for a scientifically precise calculation of the viscosity would not be met because the precondition is laminar flow. 6.2 Shear-thinning flow behavior & Anton Paar a a Figure 6.6: Flow curve and viscosity curve of water, tested in a double-gap system at T= +20 °C: Within the shear rate range shown (0.2 to 200s"), water olsplays idealy viscous flow behavior with n= 1 mPas. ‘Shear-thinning and pseudoplastic flow behavior are synonyms. This behavior is characterized by decreasing viscosity with increasing shear rates (Figure 6.7). Typical materials that show this behavior are coatings, glues, shampoos, polymer solutions and polymer melts Since viscosity is shear-dependent, it should always be given with the shear condition. Example: 1,{',) = 0.50 Pas (at 10 s) and n,(j,) = 0.10 Pas (at 100s". Measuring example: Comparison of the viscosity curves of a mineral oil and a polymer solution (Figure 6.8) Figure 6.7: Flow curve (left) and viscosity curve (right) for shear-thinning flow behavior: Increasing shear rates result in decreasing viscosity. (© by Anton Paar GmbHFlow behavior, flow curve and viscosity curve 35 5 5 Pas : os fl x pen fy = oy) é s | os 02 td “0 oat ° 0 100 200 300 400.1 500 © 200 400 6605" 1000 ¥ ¥ a Figure 6.8: Comparison of viscosity cures: Figure 6.9: Typical examole of polymer (1) shear-thinning polymer solution and solutions: flow curve and viscosty curve of (2) idealy viscous mineral of an aqueous methy cefulose solution with shear-thinning flow behavior. The flow behavior of a motor oil and an aqueous solution of wallpaper paste at an ambient temperature (T = +20 °C) was compared. The measurement was carried out as a controlled-shear-rate test. The diagram shows that the mineral oil displays constant viscosity, thus ideally viscous flow behavior. In contrast, the viscosity function of the polymer solution shows continuously decreasing viscosity indicating shear-thinning flow behavior, Measuring example: Flow curve and viscosity curve of a polymer solution (Figure 6.9). The sample used for the shear-rate-controlled test was an aqueous methyl cellulose solution at T = +23 °C, The curves show shear-thinning behavior which is typical for polymer solutions. Presented on a linear scale, the viscosity curve does not drop steeply but continuously across a large shear-rate range. Measuring example: Flow curve and viscosity curve of two emulsions (Figure 6.10) The fiow behavior of two emulsions E1 and E2 was compared at T = +20 °C. E1 was a non-diluted OW emulsion (oil in water); for E2, E1 was diluted by adding 10% water. ‘The measurement was carried out as a controlled-shear-rate test. Both emulsions display shear-thinning flow behavior, which is typical for dispersions. In comparison to many polymer solutions and polymer melts, the viscosity curves in the low shear range drop relatively steeply. At increased shear rates they flatten out in the higher shear-rate range when piotted on a linear scale. This behavior can be explained by the strong orientation of the particles or droplets of the inner phase, which already occurs at low shear rates. Most of the particles are then aligned in the direction of shear and thus cannot be orientated any further. Chapter 6by Anton Paar Grist femareie (© by Anton Paar Gmbit “0 200 400, 800 s* 1000 Figure 6.10: Typical low behavior of dispersions —_—_ Figure 6.11: Viscosity curves of three sereen- with strongly pronounced shear thinning in the printing inks with different extents of shear-thinning lower shear-rate range: Flow curves and viscosity flow behavior: The arrows indicate the shear-rate curves of two emulsions - undiluted E1, and E2 range covered by the flow cup used. In this range, with 10% water adkded. the samples do nat show any significant alfference in viscosity, Measuring example: Comparison of viscosity of screen-printing inks using a flow cup and a rotational theometer (Figure 6.11) Three low-viscosity screen-printing inks $1 to $3 with the same pigment content were compared with each other. S1 was the product used so far. It contained a known binder and showed good application behavior. S3 contained a different binder, while $2 contained a 60:50 mixture of the two binding agents. During the printing process, the three printing inks showed clear differences. However, when tested with a flow cup, the user was not able to determine any significant differences regarding the flow times of the three samples. On the other hang, the rotational rheometer was able to distinguish clearly between the flow behavior of the three samples in the shear-rate range between 0 and 1000s". The reason: Flow cups can only measure within a limited shear-rate range (in this case between approx. 200 and 400 s”). Coincidentally, the viscosity values of the three samples were rather similar just in this measuring range. Conclusion: In the case of shear-thinning behavior, single point measurements, such as with a flow cup, are not sufficient for evaluating flow behavior. 6.2.1 Internal structures of samples and shear-thinning behavior a) Polymers At rest, long, filamentary molecules of uncrosslinked polymers contract to form balls. At the edges of the molecules, the chains become entangled with each other (Figure 6.12). Under shear, the entangled balls change their shape and become ellipsoid (shaped like an American football or an airship), This deformation goes hand in hand with increasing disentanglement of the molecules. As individual molecules have less fiow resistance than entangled superstructures, the result is shear-thinning flow behavior with decreasing viscosity values at higher shear rates.Flow behavior, flow curve and viscosity curve 37 Figure 6.12: Flamentary molecules of a polymer solution or polymer mett Left: At rest with coiled and ‘entangled molecules. Right: in motion under shear, stretched and partly dlsentangled molecules, oriented in the direction of sheer. Sizes: Coiled molecules at rest have a so-called hydrodynamic diameter of between 5 and 50 nm. Example: The size ratio for polyethylene (PE) of molar mass M = 100 kg/mol, with filamentary molecules of approximate length L = 1 um = 1000 nm (when stretched) and diameter of approx. d = 0.5 nm, is L/d = 2000:1. For a better understanding, just imagine one spaghetti noodle which is 1 mm thick and 2000 mm = 2 m long (Figure 6.13) b) Suspensions containing needle-shaped or platelet-like particles In the absence of interaction forces, the particles in a suspension at rest are oriented randomly (Figure 6.74). When shear is applied, the particles start to align themselves parallel to the direction of flow. This facilitates their sliding along each other more easily. Since the individual particles now show less flow resistance than they do in an unordered state at rest, it is obvious that with increasing shear rate they display shear-thinning flow behavior with a decrease in viscosity. Sizes: Example 1: Pigment particles in metallic-effect automotive coatings, so-called aluminum flakes, have a diameter of d= 7 to 30 um and a thickness of h = 0.2 to 1 um: The resulting ratio d/h is 30:1. For a better understanding: Beer mats have a shape like this. Figure 6.13: Similar to finear polymer molucules, cooked spaghettalso resutts in many entanglements aanRip Anton pase 1 — Figure 6.14 — ! ———_ Reeate-shaped or platelet- — | like particles in a suspension: | Left: Randomly arranged at | \ i rest | Fan roton unc sry | | Geenoa nine ceston or | “A> = * Example 2: Ceramic primary particles in casting slurries such as montmorillonite (e.g. bentonite) are approx. 800 nm long, 800 nm wide and 1 nm thick. c) Suspensions with superstructures of agglomerated primary particles At rest, agglomerates in a suspension also enclose parts of the dispersion liquid thus immobilizing it (Figure 6.15). Under shear, the superstructures increasingly disintegrate into primary particles, or to be more precise, into their aggregates. As the smaller superstructures display less flow resistance, and as the formerly immobilized dispersion liquid is now free to move again, the result is shear-thinning flow behavior with decreasing viscosity at increasing shear rates. Sizes: Primary particles have a size of 1 to 10 nm, while aggregates, with a total size of up to 100 nm, are primary particles linked with relatively strong bonds. Agglomerates, with an overall size of up to 100 im, are characterized by relatively loose bonds; they consist of aggregates or particles. Figure 6.15: Particles in a suspension: Left: Agglomerated particles at rest. Right: Under shear, in motion with breakdown of the superstructure, This reduces the flow resistance, thus causing shear-thinning ifow behaviorFlow behavior, flow curve and viscosity curve 39 Figure 6.16: Droplets in an emulsion, Lett: State at rest with sphere-ke droplets. ‘Right: in mation under shear, the droplets are deformed in the dlvection of shear. 4) Emulsions with dispersed droplets Atrrest, the droplets in an emulsion are shaped like spheres (Figure 6.76). When flowing, the size and shape of the droplets are dependent on the shear applied. Increasing deformation leads to an ellipsoid shape. Because the droplets now show a smaller cross section in the direction of flow, the emulsion displays a decrease in viscosity, i.¢., shear-thinning flow behavior. Sizes: Droplets and fat particles in milk have diameters of between 0.1 and 10 ym. Remark: Emulsions with broken droplets under strong shear itis also possible that, under high shear, subdivision of droplets may occur, resulting in increased viscosity. The cause may be the increased volume-specific surface that accompanies the breakdown of the droplets. If strong interaction forces are present at the interface between the two liquid phases, this may cause undesired results. For example, a hand cream or lotion may feel sticky, tacky or stringy when applied. An interesting option for optically displaying transparent substances under defined shear conditions is the use of a rheo-microscope (Figure 6.17) Figure 6.17: Emutsion composed of water droplets in siicone oil, viewed under an optical microscope. (1) At rest, the droplets are sphere shaped (2) Ata low shear rate of 0.5 5", the droplets of the inner phase are slightly deformed (3) At a shear rate of 16 s', clearly deformed droplets are now shaped like ellasoids (ike an airshio) (4) At rest after having been subjected to a high shear rate of 100 5", which has resulted in @ breakciown of droplets a clearly reduced mean droplet size. Chapter 640 Bacranae 6.2.2 Logarithmic flow curves and viscosity curves, and zero-shear viscosity For evaluating behavior in the low shear-rate range, it is beneficial to use a log-log plot for the diagrams of flow curves and viscosity curves. This kind of a diagram is often used for viscosity curves of polymers with uncrosslinked molecules. Here, in the low- shear range, which is typically associated with shear rates below 1 s“, each of these viscosity curves shows a constant value, which is the so-called plateau value of the zero-shear viscosity n, This term was chosen because in this case the shear rate approaches zero, and therefore the state at rest. For uncrosslinked polymers at the same measuring temperature as well as for polymer solutions at the same concentration, the following applies: The higher the average molar mass M of the polymer, the higher is the value of zero-shear viscosity (Figure 6.18) Furthermore, the following applies: A steeper drop in the viscosity curve in the flow range, which occurs at shear rates above 1 s", indicates a narrower molar mass distribution (MIMD). Often another plateau value can be observed in the high-shear-rate range when almost all molecules have been completely disentangled. This value is the so-called limiting high-shear viscosity 1), which represents the viscosity at shear rates approaching an infinitely high value (Figure 6.19). The high-shear range is usually associated with shear rates above 1,000 s". 10° 10? Ign 10 1 © by non Par Gmbh 407 108 10? 107 ly Figure 6.18: Regarcing the viscosity curves of an uncrossinked polymer, the following apples io the low shear range: The higher the average molar mass M, the higher the plateau value of the zero- shear viscosity in the low-shear range. Figure 6.19: Typical viscosity function of an uncrossiinked polymer: (1) In the low-shear range showing the plateau value of the zero- shear viscostty; (2) In the flow range at ‘medium shear with shear- thinning tlow behavior: and (8) fn the high-shear range, displaying the plateau value of the limiting high-shear viscosity.