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Richard R. Eley, Ph.D. Senior Scientist ICI Paints 16651 Sprague Road Strongsville, OH 44136 The science of Rheology by definition is the study of the deformation and flow behavior of materials. Rheological science seeks to understand the relationship between applied stress and the resulting deformation or flow, particularly for materials showing non-simple responses. Applied rheology endeavors to connect fundamental properties and industrial performance for complex fluids or viscoelastic solids. Successful performance in a wide range of commercial products and industrial processes depends on meeting specific flow requirements. Paints and industrial coatings, molded plastics, adhesives, personal care products and cosmetics, inks, cement, drilling muds, ceramic slips, solder pastes, foodstuffs and medicines are examples of the range of industrial materials whose commercial viability depends on having the “right” rheology. For each of these materials, the necessary rheological properties must be defined with due regard to the flow conditions which prevail during processing and application. However, it is often difficult to link fundamental properties with real-world performance. Grounding in the principles and practices of rheology is essential to industrial scientists, engineers, chemists, and formulators who need to design products or processes involving non-Newtonian materials.
The discussion in this brief article is about protective and decorative coatings, but applies as well to adhesives, sealants, inks, and a host of commercial fluids of complex rheology. Many of these products share a common task: they must be applied to substrates and function as a thin layer. Industrial importance of thin-film fluid flow is illustrated by a few examples: • • • • • Deposition of films of controlled thickness and uniformity by blade coating, slot-die coating, direct/reverse rollcoating, spray Uniform coating of diffusive layer on controlled-release delivery systems Controlled, precise application of solder pastes and adhesives on microcircuitry boards Liquid permeation of porous materials Foam stability
The application, film formation, and defect remediation of thin, fluid layers is an important issue affecting a variety of industrial processes and products. In this presentation, we give a brief survey of some newer aspects of coatings rheology characterization. Emphasis is on interpretation of flow curve data in the analysis of coating flows associated with key application and film formation processes. We will also touch on the value of viscoelastic properties to the foregoing, viscoelastic characterization by creep analysis, and the potential for more detailed understanding offered by computer modeling of coating flows.
The understanding of coating performance in terms of rheology is still far from complete. A final film of uniform thickness implies good flow and leveling and the avoidance of defect development in the course of film formation. In fact. Rheology and Performance Generally. Reduced-VOC aqueous coatings have consequent higher surface tension and stronger Marangoni effects. geometric and rate factors of the application process. therefore. For coatings. for certain reasons. the array of solvents from which to choose was large. surface tension gradients. rheology determines success for coatings. Moreover. Modern rheological instrumentation is helping to achieve that goal. and film formation were relatively straightforward to achieve by solvent selection and blending. Experienced formulators say that more than half the cost of new product development is consumed in “getting the rheology right”. Among these reasons are (a) the sheer complexity of coatings processes. while reducing the number of formulating options and at the same time generating a host of performance/application problems. the process of application and film formation obviously requires not only a large total deformation. a problem that will obviously require urgent resolution. which complicates the understanding of the role of rheology in process outcomes. and (b) difficulty in linking measured fundamental properties with real-world performance. complexities of substrate geometry. Achievement of this goal is complicated by complex rheology. pigment dispersion stability. apparently “minor” changes in a raw material or process can cause significant and unexpected variability in product rheology. The large-scale move toward environmentally compliant coatings (waterborne.or zero-VOC) has in general resulted in more complex rheology. For all these reasons. A sophisticated fluid dynamics model should take account not only of .Relevance of Rheology to Coatings Formulation To a degree matched by few other materials. Control of rheology. higher solids. and (b) are relatable to the critical processes that paints must undergo. or substrates having sharp edges or small radii of curvature (holes or sharp corners). a prime success criterion is the achievement of a uniform coating layer during the film formation and solidification process. substrate wetting. reduced. To meet the latter objective requires characterization methods that cover a wide range of stresses and time scales. open time. in order to achieve success. In the times when the majority of paints and industrial coatings were solvent-borne. Though all other properties be acceptable. a coating will usually not meet with success if the rheology is not. but also a high degree of control of flow. rheological analysis is a vital and cost-effective tool for the coatings industry. which make it more difficult to coat substrates of lower quality (lower or less uniform in surface energy). Difficult pigment wetting and stable foam are other consequences of reduced solvent content. the achievement of solventborne-like flow and appearance in a waterborne system has remained an elusive target. is to develop methods of rheological characterization that (a) yield accurate data for complex fluids. One answer to the dilemma is computer simulation of coating processes. which utilizes the fundamental rheological data as the required input. and provided great latitude in formulating for performance. Flow cannot be controlled unless it can be properly measured. and environmental factors. The objective for the applied rheologist.
Haake CV. Principles and methods of rheology in coatings. In general. 33. For non-Newtonian materials. In a controlled-strain instrument the angular displacement (or the angular velocity) is the independent (controlled) variable and the viscous drag-torque the dependent (measured) variable. . but a material function— in this case. Philadelphia. it is not readily accessible. The difference is in whether the torque or the angular displacement is the controlled variable. (2000). a “function” of the shear rate (or shear stress). and other suspensions of particulate solids at useful concentrations will be nonNewtonian. emulsions. R. Meyers. A plot of viscosity against shear rate or shear stress (normally log-log) may be termed a “flow curve”. and because of other more fundamental 12 shortcomings. Fortunately. environmental factors. The following sections will elaborate on these points. in Encyclopedia of Analytical Chemistry: Instrumentation and Applications. R. R. the viscosity is no longer a material constant. Eley.coating rheological and physicochemical properties but also of process details. many coating problems can be understood and solved from shear viscosity and viscoelastic data alone. Detailed discussions of these important topics. Normally. the TA Instruments Weissenberg Rheogoniometer.. and Bohlin CVO. as well as definitions of rheological terms can be found in  and  and references therein. mechanisms of shear thinning and shear thickening. ASTM Paint and Coatings Testing Manual. Eley. Controlled Stress and Controlled Rate One has a choice of working principles in modern rotational rheometers: either “controlled strain” (or controlled strain rate) or “controlled stress”. while computer modeling is perhaps the ideal approach. a viscosity measured at a single shear rate is not an adequate representation of the rheology of the system. provided the experiments performed are well designed and the results properly interpreted. Instruments of the 1. For this reason. 333-368. For nonNewtonian fluids. 14th ed. Ed. and may be generated using equilibrium or non-equilibrium flow measurement methods. and yield behavior. Chap. irregular substrate geometry. for example. such as the viscosity as a function of shear rate or shear stress.. “Controlled-stress” instruments in actuality control the torque. Ltd. 1995. Non-Newtonian Behavior Commercial fluid products comprise a wide variety of materials. “Research-quality” rheometers measure some rheological property.. Wiley & Sons. a curve will be produced representing the functional dependence of the measured property. with a wide range of consistencies. Instruments of the controlled-strain type include. with emphasis on the understanding and interpretation of steady-shear flow curve data. and measure the resulting angular displacement. colloidal dispersions. R. the rugged but simple “single-point” viscometers commonly used in the industrial laboratory are generally not well suited for the characterization of non-Newtonian fluids. ASTM. body forces (gravity and centrifugal force) and changes in properties with evaporation and temperature.. 2. A. Rheometrics ARES. polymer solutions and melts (above Mc).2 We will neglect here the subjects of rheological models. Rheology and viscometry. R.. J. However. or material function. .
solder pastes. which can be calculated from the forces acting (e. the more “natural” way to characterize coatings and other complex fluids. printing ink. medicines. Haake RS. an advantage of its typically stable torque capability and high angular resolution. but rather the observed shear rate is the resultant of the stress driving the process and the corresponding viscosity at that stress. drilling muds. Structured fluids tend to be “shear-sensitive” (more precisely. directly measure the stress at the onset of yield. CR instruments impose a shear-rate sweep while measuring the drag-torque response of materials. There is an important point to be made in regard to the role of rheology in coating flow during application and leveling. a test mode which allows materials to “obey their own rules” of stress-strain response.controlled-stress type include the TA Instruments AR-1000. pigment and colorant dispersions. fluid structure tends to collapse rapidly. CS instruments can. edge withdrawal). the rheological response to those forces determines the resulting coating flow. with the shear rate a rheology-dependent variable. as strain increases exponentially under a linear strain-rate sweep protocol. etc. sagging.. foodstuffs. CS instruments are especially useful for characterizing structured fluids and granular dispersions such as paint. coating flows are not “driven” at a characteristic shear rate. gravity and surface tension) and . Taking coating flows as a case in point.. ii) many industrial flows are governed by the available shear stress. coal slurries. adhesives. Consequently. as well as in undesirable flows which may lead to film defects (e. iii) separation between flow curves is always better as a function of shear stress (more sensitive variable). It is that these flows are driven by specific shear stresses. controlled-stress (CS) instruments can measure much lower angular velocities than can controlled-strain-rate (CR) instruments. the usual practice is to plot with shear rate as the independent variable. Rheology of Coating Application and Film Formation In graphing the viscosity flow curve. Rheometrics SR5. Therefore. and iv) the collapse of particle flocs or gel networks is more obvious. Using stress as the controlled or independent variable is. cement. avoiding errors associated with extrapolation or curve-fitting methods. and Physica MC rheometers. CS is better suited to measure long relaxation times. In terms of performance.g. The choice between them depends on the material under test and the intended experiments. coating flows are the outcome of the sum of forces acting on a fluid coating layer. in this sense.g. but CS instruments tend to be more limited at the high angular velocity and oscillation frequency end. Bohlin CSR. First of all. with the result that relatively few data points are obtained to provide information on structure. This is particularly true where materials exhibit apparent yield behavior. it is important to realize that the proper variable for correlating coating rheology to real-world coating processes is the shear stress. CS devices use linear (and logarithmic) rates of stress increase. That is. We prefer to use the shear stress as the abscissa for several reasons: i) the torque (shear stress) is the independent variable for the rheometer used. personal care products and cosmetics. crawling. strain-sensitive). in principle. ceramic slips. cratering. In contrast. Each of the two main instrument types has characteristic advantages and limitations. not the shear rate.
The sagging shear stress calculated from Eq.. however. Not to do so is wrong in principle and will result in incorrect comparisons of paints with respect to their relative rates of. (ii) surface tension-driven leveling of surface roughness.the geometry of the film [1. Note that process shear rates are shifted to the left for the higher viscosity paint. are not the same. e. The shear stress acting on a coating layer (for a given process) is independent of the rheology. 1 compares two paints in this manner. depending on the coating’s viscosity at the acting shear stress. In a typical paint development laboratory. The shear rate is a dependent variable. the shear rate will be dependent on paint rheology. density. particularly when flow curves cross over. no matter what the rheology of a paint. comparison of viscosities measured at arbitrary shear rates can lead to incorrect predictions of relative sagging behavior. sagging. Plotting with shear stress as the independent variable. (1) determines the viscosity controlling sagging (ηsag) from the flow curve. Fig. paint A is about 50% higher than B. Sagging is driven by gravitational shear stress σ g whose magnitude depends solely on the wet film thickness h and density ρ (g is gravitational acceleration): σ g = ρgh cos θ (1) (cos θ =1 for a vertical substrate). with gravitational shear stress levels corresponding to 3 mils wet film thickness indicated. shear stress. 2 shows flow curves for the same two paints plotted as a function of shear rate. pigment settling. which is the more common practice. depending on their rheology. Comparison of coating rheology as a function of shear stress both simplifies the process and is more correct in principle. The viscosities of the two paints at the Stormer shear rate are about the same (Paint B actually slightly higher). The shear rates for these processes. shear stress plots. Fig. The solid vertical line in Fig. using the Stormer viscometer and the so-called “ICI Cone and Plate Viscometer”. surface tension). the shear stress acting on a coating layer for a given process is the same (for a given geometry. for real processes. This issue is key to using flow curve data correctly to understand coating performance. 1. However. allows straightforward and correct comparison of paints A and B at the specific shear stress for a particular process. these processes can occur over a wide range of shear rates. Predictions of sagging from comparison of viscosities measured at an arbitrary shear rate will be misleading because paints sag at different shear rates. leveling. and (iii) application by brush or roller. 2 approximates the shear rate of the Stormer viscometer. At an arbitrary shear rate of 1 s-1. as opposed to viscosity vs. rather than shear rate. 1. Clearly. as illustrated in Fig. 2. Fig. Fig.g. The key question to ask is whether such a two-point method adequately represents paint rheology. this time with the viscosity plotted as a function of shear rate.2]. 2 . with the calculated sagging shear rates at 3 & mils indicated ( γ sag = σsag / ηsag ). as in Fig. or ease of application. The appropriate independent variable to use to differentiate the performance of paints in terms of their rheology is the shear stress. whereas at the actual sagging shear stress or shear rates paint A is 600% higher in viscosity. rheology is characterized by a “two-point” method. 2 shows the same two paints as in Fig. The proper way to predict relative sagging tendency is to first select the governing viscosity from a plot of viscosity vs. The process stresses illustrated in the Figure are for (i) gravity-driven sagging of a 3-mil wet film. For this reason it is preferable to represent flow data as viscosity vs. The point is that. In contrast. shear rate.
Clearly.000 10. one mildly shear thinning.0 1000 shear stress (dyne/cm^2) Leveling stress 10000 Figure 1. 2 are vertical dashed lines indicating shear stresses driving several important film formation processes.000 0. 1000 B A Brushing/rolling stress viscosity (poise) 100.shows flow curves for two paints. leveling. 6. color. while the other shows evidence of a sudden structural collapse at a shear stress of around 250 dyne/cm2. It is apparent that the Stormer and ICI data points are located in the “sheared-out” region of the paint rheology curves.1000 1. leveling of surface waviness.0 10. the two-point characterization method would give no information about the leveling/sagging/pigment settling regimes at all.00 3-mil sagging stress 1.00 100. Presence of the latter will have profound effects on sag. opacity. . pigment settling. Also shown in Fig. etc. and 12 wet mils film thickness. Superimposed on the curves are points indicating the corresponding measurements from the Stormer and ICI viscometers. (iii) brushing/rolling application. (ii) surface-tension-driven leveling stress. and gravitational sag at 3. shear stress plot for two paints A ( ) and B ( ). The two-point method also misses the region of high structural viscosity due to flocculation. Viscosity vs. Vertical dashed lines indicate (i) gravitational shear stress driving sagging for 3-wet-mil paint layer. namely.
0 shear rate (1/sec) 100000 Figure 2. Vertical dashed lines indicate shear rates for each paint and process. shear rate plot for paints A ( ) and B ( ). .1000 Leveling shear rates viscosity (poise) 100. application are different for A and B.000 Stormer shear rate B A 0.1000 0.00 1. Vertical solid line is the approximate shear rate for the Stormer Viscometer.0 Sagging shear rates Application shear rates 10.000 100. Shear rates for sagging.01000 1. shifted to left for higher-viscosity paint. leveling. Viscosity vs.