‘Advanced Testing and Characterization of Bituminous Materials ~ Loizos, Partl, Scarpas & Al-adi (eds) © 2009 Taylor & Francis Group, London, ISBN 978-0-415-55854-9. The morphology of SBS modified bitumen in binders and in asphalt mix H. Soenen Nynas N.V., Antwerp, Belgium X. Lu, & P. Redelius Nynas AB, Nyndshamn, Sweden ABSTRACT: The morphologies of SBS modified binders and their asphalt mixes were studied using fluorescence microscopy. In a first part, the morphology of an SBS polymer in different bituminous binders was investigated as a function of the preparation method, in particular as a function of the cooling rate and isothermal annealing periods. Storage stable and unstable SBS-bitumens, as defined by the tube test after 3-day at 180°C, were selected, The microscopic observations showed that the morphology strongly depends on the thermal history of the respective samples. These microscopic observations are supported by the dif- ferences seen in the rheological properties and in the force ductility curves of the respective binders. Ina second step, the morphology of the SBS binders was investigated directly in the cor- responding asphalt mix. The morphology was studied in compacted specimens as well as in the loose mix using several preparation procedures. Asphalt specimens were sliced in plane or alternatively in thin sections according to the methods developed by the Danish Road Institute, Also cold fractured asphalt surfaces were investigated. The analysis of the asphalt surfaces showed clearly that the morphology in the asphalt mix was very similar for all the binders tested, and was in most cases rather different from the morphology observed in the binder specimens. In the asphalt mix, the SBS phase is located in separate and distinct domains; this was observed for all the mixes tested. The observations suggest that the differ- ences in PMB morphologies between compacted asphalt and binders is an important factor that should be considered when investigating the properties of polymer modified binders, and especially when searching for performance related binder tests 1 INTRODUCTION Itis quite well known that most polymers commercially used like SBS and EVA, are only partially miscible with bitumen (Kraus, 1982). It has been demonstrated that phase separa- tion occurs upon cooling the binder from the high production temperatures (180°C. 200°C), Even at these high production temperatures some polymer modified bitumen (PmBs) may already show phase separation. The extend of this phase separation is dependent on the bitumen type, the concentration of polymer, and the characteristics of the polymers, for which the polymer molecular weight is certainly an important one. Some literature reports have indicated that the morphology in PmB binders is dependent on the thermal history of the binders, like the cooling conditions. It is also known that the morphology can have an influence on some physical properties of PmBs, properties like the rheological behavior and the force ductility. (Brilé et al. 1988, Dony & Durricu 1990, Pasquier et al. 1997, Mouillet et al. 2004, Soenen et al. 2008) The purpose of this paper is to demonstrate how the morphology of PmBs depends on the sample preparation method, how this can be investigated, and to show how large these effects can become. Furthermore, this study also shows how the morphology obtained in a 151small binder sample can differ from the morphology of the same binder when it is embedded in a (necessarily larger) asphalt mixture structure. This observation is important, since physical properties of polymer modified binders, like the softening point or the rheological behavior, are dependent upon the morphology of the phase structure. And as many performance indicator tests for binders are studied on small sample volumes, for example in a plate-plate rheometer, the morphology in these small samples can be very different from the morphology that is finally obtained in the asphalt mix. This observation can be an explanation why binder performance indicators that often work well for unmodified binders only partially work for PmBs 2. EXPERIM) 2.1 Fluorescence microscopy The morphology was studied with an epi fluorescence microscope. This microscope was a Carl Zeiss Axioskop 40Fl, equipped with a digital camera, deltapix DP200, The exposure time of the camera can be changed from a few ms up to 6s, due to slight variations in this exposure time, the colors in the graphs can slightly vary as well. The UV light source comes from a high pressure mercury arc lamp HBOSO. The microscope uses a three filter system; an excitation filter, a beam splitter and an emission filter. From the light source, the light first goes through the excitation filter which transmit light with a wavelength between 450 to 490 nm. Light of this wavelength hits the surface of the specimen, part of this incident light is reflected and a part is emitted by the sample. The emitted light has a longer wavelength than the incident light. Reflected and emitted light will hit the beam splitter, where only wave- lengths longer than 510 nm are transmitted, Finally this transmitted light hits a third filter which has a high transmission for wavelengths longer than 515 nm. Magnifications levels of 50x, 100x and 200x are available. The microscope is also equipped with a Mettler hot stage, which allows to investigate samples at elevated temperatures, or dur- ing controlled heating and cooling 2.2 Samples Four PmBs were used, referred to as PmB1 to PmB4, and the base binders were derived from different crude origins. All base bitumen were of the 70/100 type. A linear SBS triblock copolymer was used in the preparation of the PmBs. The SBS had a weight average molecu- lar weight of 189000, the fraction of tri- versus diblock copolymer was 0.8, and the styrene content was about 30%. The polymer was supplied by Kraton Polymers, type name Kraton D-1101CU. CU refers to the fact that in this polymer silica powder was not added, this pow- der also gave a signal in the fluorescence microscope. PmBs were made in 5% SBS concentra- tions, conventional properties of the blends and also results of the storage stability tests are summarized in table 1. The storage stability test refers to the tube test, (EN 13399) in which a tube of PmB is stored in an oven at 180°C for 3 days, afterwards the softening points of the top and bottom fractions are investigated. Blends were prepared by mixing polymer and bitumen at 180°C, stirring was continued for 3 hours at a speed of about 500 rpm. Table 1, Overview of the PmBs used, Tube test-3 days at 180°C Pen 25°C R&B Top-R&B Bottom-R&B AR&B PmB dum Cc °c Cc Cc PmB1 37 76.0 94.5 69.0 255 PmB2 52 85.0 36.5 86.5 0 PmB3 56 118 54.6 55.6 10 PmB4 52 65.0 34.2 52.2 32.0 1522.3 Asphalt mix type ‘The asphalt mixture was a dense graded asphalt concrete (Swedish standard ABT 11) with a maximum aggregate size of 11 mm. A crushed granite material was used, the nominal binder content was 6.5% by weight, and the void content was about 3%. Asphalt specimens were compacted using the gyratory compactor, to the desired density, which means gyrations vary slightly from specimen to specimen. The mixes are referred to as M1 to M4. Different meth- ‘ods were used to visualize the morphology of the PmB in the asphalt mix. These methods will be discussed in section 4. 3 MICROSCOPIC OBSERVATIONS IN THE BINDERS SAMPLES 3.1 Drop method In this procedure, samples for the microscope were prepared by taking a small drop from a (hot) can, and by letting this drop fall on a cold glass plate. After cooling to room tempera- ture, which only took a few seconds, the samples were viewed through the bottom plate. This procedure is often used in literature, since it is very simple. In this procedure the sample is necessarily cooled very quickly to room temperature, because the volume of the drop is very small, and the glass plate is at ambient temperature. So one can assume that the morphology obtained in this way is similar to the morphol- ogy present at the moment the sample is taken. Photographs of morphologies are shown in figure 1. In this figure, the temperature refers to the temperature in the can, at the moment the drops are taken out. This temperature was varied from 200°C to 120°C, as follows: A can was first heated to 200°C, and after 10 minutes a drop was taken. Afterwards, the same can was cooled to 180°C, and again after 10 minutes a drop was taken. This procedure was 200°C 160°C 160°C 140°C Temperature 420°C “PmB1 — PmB2 Figure I. Morphologies of drops of samples, the temperature of the can when the drops were taken is indicated, as well as the PmB type (magnification = 200s). 153repeated until 120°C. Below 120°C it became difficult to take a drop of sample, During the procedure, the can was continuously stirred by a mechanical stirrer, and therefore, sometimes orientation effects are obvious. From figure | it is quite clear that all the Pmbs show a less distinct polymer phases when the temperature is higher. This corresponds to the general knowledge that SBS type of polymers become more compatible when temperature is higher. At high temperatures differences depending on the type of base binder are clear, some already have a homogene- ous appearance when the temperature is at 160°C, while others are even at 180°C not fully homogeneous. However at lower temperatures, 120°C, the binders all have a phase separated structure even though the samples were stirred, and all have a very similar appearance. In this respect it needs to be noted that homogeneous refers to the resolution of the micro- scope, which is for this particular magnification limited to about 2 micrometer. With this resolution, it is not possible to observe a phase separation between the styrene and the buta- diene blocks of the SBS copolymer, since this occurs on a smaller length scale. 3.2. Thin film method If the drops of PmB, taken on a cold glass plate, are reheated, they start to flow and form a thin film, An example of such an experiment is shown in figure 2. In figure 2, a drop of PmB2 was taken from a can at 200°C, and was afterwards reheated to 140°C. It is quite clear that at this temperature the mobility is high enough to start a phase separation. With time the phase separation continues, smaller polymer phases coagulate and become larger, and more distinct. This experiment was repeated for all the binders, at various temperatures. In figure 3 the morphology after isothermal annealing for 1 hour at the indicated temperatures is shown Again clear differences at higher temperatures are obvious, some binders still have a homo- geneous appearance at 160°C, while others do not. At lower temperatures (120°C), all the morphologies after | hour annealing, show distinct polymer-rich and bitumen-rich phases, and the bitumen forms the continuous phase. At ambient temperature, and slightly higher, tested up to 60°C, the morphology remained constant and did not change isothermally. 3.3. Freeze fractured samples ‘The PmBs were also investigated using the freeze fracture method, which is described in EN 13632. According to the norm, specimens have to be prepared by pouring an amount of sample in an aluminum mould which is completely surrounded by a sand bath. The mold, the sand bath and the binder have to be at a high temperature. After filling, mold and sand bath, should be left to cool to ambient. In this way a controlled (and because of the large volume a rather slow) cooling of the sample is obtained. Afterwards the mold is cooled to a low tem- perature (a temperature where brittle fracture is obtained), and after fracturing, the fractured surface is investigated. This method gives a picture of the undisturbed bulk structure cass Figure 2. Morphology of PmB2 after isothermal annealing at 140°C. The annealing time is indicated, ‘The starting sample was taken at 200°C (time = 0) (magnification = 200x), 154Figure 3. Morphologics after | hour isothermal annealing. The annealing temperature and the binder type are indicated. ‘The starting sample was each time taken at 200°C (magnification = 50x). In this paper, this procedure was not exactly followed, since silicon molds were used with a diameter of 2.5 cm. These molds were in fact the same as the ones used to make samples for testing in a rheometer, with the 25 mm plates. Different cooling rates were obtained: first by just leaving the mold after filling to cool to ambient, secondly by leaving the molds for an hour at 120°C, and finally by leaving the molds in an oven with a controlled cooling rate of 2°C/min. In figure 4A, the freeze fractured morphologies obtained after different cooling procedures of the molds are shown. In these experiments, the PmB was taken form a hot can (200°C) and was manually stirred. 3.4 Rheology and force ductility of the binders In this section, it is investigated if the different polymer structures have an influence on the mechanical properties of the binders. Two tests were evaluated, rheological measurements and force ductility tests. Black curves are shown in figure $ for two of the PmB samples, after several preparation procedures. In this respect the procedure denoted as standard refers to the conditions normally used when preparing samples for the DSR rheometer: a cold silicon mold is filled with hot binder (in this case taken at 200°C) and is left to cool to ambient. The theological test after annealing at 120°C are different and may be related to the differerent morphologies. Especially for PmB2, the effects are large, and the effects are also larger in the lower modulus region or at higher temperatures (50°C-80°C). For PmB2, the specimen pre- pared according to the standard procedure has a rather homogeneous morphology and the polymer forms an entangled network throughout the sample (in figure 4, the freeze fracture after quick cool). The presence of this network gives a rubbery-like behavior. For a dry poly- mer this rubbery-like behavior (entanglement region) is around modulus levels of 10° Pa. In this case, as the rubbery phase is swollen with components from the base binder, the modulus level is reduced to around 10%, 10 Pa, what also corresponds to a phase angle of 40-60°. After leaving the binder for some time at 120°C however, the polymer is concentrated in 155Freeze fracture after quick cool (Gust leaving the mold to cool to ambient) (200x ‘magnitiation) (tm Freeze fracture after cooling at =2°Cimin (50x magnification) Freeze fracture After Ih at 120°C (50x magnification)} Binder PmB2 PmB3 PmB4 Figure 4. Morphologies obtained after freeze fracture. The thermal history of the PmBs and the type le are indicated of samp! Figure. Black curves of two PmBs as function of thermal history of the specimen. Standard procedure indicates filling a cold silicon mold with hot binder and leaving it to cool to room temperature, fe Ee oe == : poles ee “eam Figure 6. Force ductility curves for two of PuaBs, afer different preparation conditions. separated domains and the entanglements are now only in the separate droplets, surrounded by a bitumen-rich continuous phase. In this morphology they cannot provide a large elastic effect. For PmB1, the morphology after quickly cooling the binder was already somewhat disperse (figure 4), showing very small polymer-rich droplets so in this case even after quickly cooling the specimen there is already less effect of the polymer network 156In figure 6, force ductility curves for two PmBs are shown, and the differences due to the preparation methods become obvious at long elongations. After standard cooling, the morphology of PmB4 is already phase separated, figure 4, so the starting elasticity for this PmB is lower compared to PmB3, which has, after standard cooling a rather homogeneous appearance. When the binders are stored at 120°C, phase separation starts (PmB3) or continues (PmB4), and ductility levels decrease. So in conclusion, the differences observed in the morphology of the PmBs and the influences due to cooling rate and isothermal annealing are confirmed in the mechanical properties of these binders. 4 MICROSCOPIC OBS! ERVATIONS OF THE PMB IN AN ASPHALT MIX 4.1 Morphologies of plane and thin sections Initially, in this project, we tried to observe the polymer phase in a relatively thin, 1 em, stand- ard sawed asphalt slice. However, it was not possible to investigate the binder morphology in such a specimen, since there was too much fluorescence from the stone surfaces and from other stone material. And since the surface was not flat enough, it was impossible to have a larger part of the structure in focus. In 1999, the Danish Road Institute published a report on the morphologies of PmBs in binder and in mixture tests (Wegan, 1999). They also developed a method to prepare plane and thin asphalt slices. The preparation method is described in (Wegan, 1999), but a short summary of preparing a thin slice is given below. The asphalt mixture is first cut with a dia- mond saw (3.3 mm blade thickness) from an asphalt core. A smaller asphalt specimen is cut, approximately 30 x 45 mm and 10-20 mm in thickness, by means of a thinner saw (1.3 mm blade thickness). The specimen is then glued onto a plane glass slide, which helps to attach the specimen, The specimen is then impregnated under vacuum with a colorless epoxy resin, which after curing helps to stabilize the specimen during further preparation procedure. The surface is sawed further, ground to levelness by diamond coated rollers. An object glass is glued to the surface of the specimen, which is the first finished side of the thin section. The specimen is further cut, ground and polished to a final thickness of 20 um. Throughout the preparation procedures the specimen and equipment is constantly cooled to approxi- mately ~5°C to avoid smearing of the polymer phase. The Danish Road Institute agreed to prepare thin slices from the asphalt cores containing the four PmBs selected for this study. In figure 7, photographs from these thin slices are shown. In addition to the four PmB mixes, an unmodified mix is added as a reference. From figure 7, the areas with large fluorescence are due to the stone surface, and they are of little interest, and are mostly outside the image. But the mastic phase in between the stones, shows small spots which are probably polymer rich phases, these are not present in the reference mix. From figure 7, we can observe that for the 4 PmB mixes, the polymer phase is for all samples in separate domains, and the bitumen-rich phase is the continuous one. 42 Other methods Other ways of investigating the morphology in the asphalt mixture were tried. For example, we also looked at the morphology of a piece of mix that was freeze fractured, in a similar way as the binder samples, The advantage of this method is that there is no or only very limited interference from stone surfaces. Since at least for this type of mixtures, the fracture was within the mastic phase, Results are shown in figure 8. Again we can observe the polymer- rich phases as distinct droplets. The result is very similar to what was observed for the thin sections. But as is also obvious from figure 8, there are area’s out of focus, since the surface after fracture is uneven, and in this case we did not apply any method to flatten it. Finally, we also looked at the surface of the loose mix as such, and also in this case there is no interference from the stone material (except if the coating would not be good). The results are also presented in figure 8, and we see again that the polymer phase is present in distinct domains. But, in this case the domains seem to be somewhat larger compared to those in the 157Thin sections sliced from) asphalt cores ref, mix Figure 7. Microscopic observations in thin asphalt sections, prepared by the Danish Road Institute (magnification is 200%). compacted asphalt cores. The reason for this is due to the larger sample amount in the loose mix, when it was prepared and the consequently slower cooling rate. Finally in figure 9, a comparison is made between the morphology of the mix after a nor- mal cooling of the loose mix, and after storing this mix for 4 hours at 135°C. These condi- tions were chosen since they are sometimes used to simulate a short term aging of the mix. It can be observed that also in the mixtures, the phase separated domains increase after isother- ‘mal annealing. So some care is needed when applying isothermal procedures to PmB mixes 5 DISCUSSION In this study, three methods to test the morphology of bituminous binders were used and compared. Each method has its advantages and limitations. It was also shown that the mor- phology observed in binder specimen, after different thermal treatments, was in agreement with the results of rheological and force ductility tests. Methods to measure the morphology in the asphalt mix have been presented; It seems from these investigations that studying thin asphalt mix specimens gives a similar result to measurements on the fractured asphalt mix. Even loose mix can be used, although the mor- phology can be different if the thermal treatment of the mix is different. In the thin sections, the whole surface can be brought in focus, but there is also interfering fluorescence from stone material and it is not 100% sure that the sample treatment did not influence the mor- phology. When looking at fractured surfaces the surface is not flat, so there are areas in the photographs that are not in focus, but all fluorescence observed comes from the polymer phases. And one can also assume that disturbances in the morphology duc to fracturing the samples are limited. In this study all the binders finally showed a phase separated structure in the asphalt mix, independent of the base binder used. Even for PmB2 and PmB3, which were storage stable, the morphology in the mix was phase separated. The storage stability has certainly an effect on the morphology at high temperatures and also after quickly cooling a small specimen, ‘The two storage stable PmBs (PmB2 and PmB3) were in the drop method and the thin film morphology compatible to lower temperatures than PmBI and PmB4, But in the final mix morphology the differences between these four binders were very limited. It should be noted that the morphology also depends on the polymer concentration, the polymer molecular weight and structure, and these parameters were not varied in this study, In this paper, we showed that the cooling rate, and by this the sample volume of a specimen can play a role in the morphology, when working with SBS modified binders. And the mor- phology can in turnalso influence the mechanical properties. In tests, using small specimens the chance of having a more homogenous morphology is larger, and in those tests the mechanical behavior can be different than in tests using large specimens, where the bulk sample is cooled slowly. In the European norm for the visualization of polymer dispersions (EN 13632) a slow cooling rate is obtained. Since, the sample has to be poured in an aluminum mold, which is in turn surrounded by a sand bath of about 600 ml content. The mold and the sand bath have at the time the sample is prepared, the same temperature as the binder. And according to the 158‘Fractured surface, ater ucturing asphalt ed Surface ofa coated, fiom Tose mix Figure 8, Microscopic observations from fractured compacted mix samples, and from loose mix samples (magnification is 200%), "Tests on loose mixtures 1. after undisturbed (normal) cooling from a larger pile 2. after 4 hour at 135°C (procedure sometimes used to short term age the mix) Figure 9. Microscopic observations from loose mix samples (magnification = 100x), norm on sample preparations (EN 12594), for a PmB this temperature needs to be between 180°C and 200°C. The reason for this rather complicated procedure is to obtain a thermal trajectory in the binder that is close to what is obtained in an asphalt core. If this slower cool- ing is needed to investigate the morphology, it should also be interesting to apply this prepa- ration method when testing mechanical properties on SBS modified PmBs. There are a lot of test methods where small and even very small sample specimens are used: for example the specimens in rheological testing, in the Fraass breaking point, in the ring and ball softening point can be considered as very small and also the samples for force ductility and the bending ‘beam rheometer can still be considered as small, compared to an asphalt mix. This paper wants to encourage investigations on morphology, especially when they can be cartied out directly in the asphalt mix, since there is a need to have more insight in the phase morphology of mixes as they are placed on the road These investigations can also help in revealing possibly new mechanisms by which the addition of polymers can influence asphalt performance. At this stage little is known how a distinct polymer phase, located in separate domains can play a role in for example crack initiation, or in crack growth. Knowledge of these aspects can help to optimize PmB formulations with respect to performance 6 CONCLUSIONS In this paper, the morphology of four SBS modified binders and their corresponding mixes, was investigated, and the main findings are summarized below. It was shown that the morphology of the binders depends on the thermal treatment of the samples, cooling rate, isothermal annealing, and even stirring can have an effect. 159At lower temperatures, below 60' anymore with time. the morphology in the drop method relates to the morphology at the time the sample is taken, because of its very small volume and correspondingly high cooling rate. — the freeze fracture method can be used to investigate the morphology in larger binder samples, different cooling rates or isothermal annealing can be applied by modifying the procedure, — the morphology in a binder sample, obtained by changing the thermal history of the bind- ers also has a clear influence on the mechanical properties measured by force ductility and by rheology. the morphology in the asphalt mix can be investigated by either preparing thin sections, or simply by investigating the fractured surface of a broken mix. This conclusion is at this moment still preliminary since it was only tested on these four mixes. —As the morphology depends on the cooling rate, it will also depend on the size or volume of the investigated specimen. Since asphalt cores are often much larger than binder samples, the cooling rates in an asphalt mix sample are very often slower compared to cooling rates ina binder sample. The difference in cooling rate between binder specimen and asphalt mix cores can have a strong influence on the phase morphology. As morphology influ- ences the mechanical properties, this conclusion can have important consequences for the relation between binder and mixture properties. If in both tests (binder versus mix tests) the morphology of the PmB is different, it would be rather surprising to find a good cor- relation between these tests For all four mixes investigated, the morphology in the mix is observed as a phase separated structure with distinct polymer phases in a continuous bitumen-rich matrix. The question if a binder is storage stable at high temperatures, does not seem to have an influence on. the final morphology in the mix. In mix tests, the morphology is also dependent on the thermal treatment of the mixtures. This should be taken into account when performing for example mix aging tests at 135°C on loose or on compacted mixtures the morphology in binder samples is not changing REFERENCES Brilé B, Brion ¥., Tanguy A. 1988. Paving asphalt polymer blends: relationship between composition, structure and properties. AAPT 57: 41-64. 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