‘Advanced Testing and Characterization of Bituminous Materials ~ Loizos, Partl, Scarpas & Al-adi (eds) © 2009 Taylor & Francis Group, London, ISBN 978-0-415-55854-9. Aging of SBS polymer in hot and cold bituminous coatings. Relationship between microstructure and performances: Low temperature and cohesion properties C. Gueit, M. Robert & G. Durand COLAS S.A, Campus Scientifique et technique, Magny les Hameaux, France ABSTRACT: It is well known that SBS polymer modified bitumens (PMB) exhibit better performances than pure bitumens. But to what extent are these performances remaining after Jong term aging on site, as well for hot asphalt mixes as for thin layer coatings? In order to answer to this question, a laboratory study has been performed on several PMB on the one hand and on different types of recovered binders from modified (PMB or latex) emulsions on the other hand: we focused respectively on low temperature properties meas- ured by BBR (Bending Beam Rheometer) and DIT (Direct tensile strength Test) methods, and on cohesion and elastic recovery tests. Long term aging is simulated by using RTFOT (Rolling Thin Film Oven Test) followed by PAV (Pressure aging vessel) Simultaneously, we monitored the evolution of polymer characteristics from the initial stage to the aged stage in term of microstructure and more especially in terms of intrinsic molecular weight properties. For this assessment we carried out GPC (Gel Permeation Chromatography) experiments that consist in separating molecules according to their size on a porous matrix. The conclusions of the study are the following ones: SBS js still present and active after aging: only a moderate evolution in polymer molecular size occurs after long term aging. ‘These observations can be correlated with a small decrease in low temperature and cohe- sion performances for the aged binders compared to initial ones. Elastic recovery is not relevant in the context of strongly aged binders. — Performances remain far better than without SBS. This confirms the observations on site too, 1 INTRODUCTION Due to its characteristics, a bituminous binder guarantees the longevity of road paving. It is therefore chosen or formulated according to its ability to withstand various types of stresses on the road. Replacement of pure bitumen by a polymer-modified binder, particularly using SBS, allows its scope of application to be extended (Corté et al. 1999). In the case of asphalt mix, the thickness of the surface layer may be reduced: Thin asphaltic overlay, usually 3 to 4 cm thick, may be replaced by Very thin asphaltic overlay (2 to 3 cm) or even Ultra-thin asphaltic overlay (1 to 2 cm). Furthermore, the field of application for Thin asphaltic overlay (3 to 4 cm) may be extended to damaged or deformed surfaces. In addition, use of modified bitumen is vital in the case of porous asphalt, where contact surfaces between aggregates are reduced. In surface coatings, in the form of anhydrous or emulsion binders, the presence of a poly- mer in the binder allows them to be applied on high-traffic road surfaces with many curves, Lastly, used as an emulsion, a modified binder improves the effectiveness of a bonding layer. In all cases, the longevity of the surface depends on the resistance of the binder, which undergoes two types of aging: rapid “construction” aging (transit via the coating plant, appli- cation), and slow “service” aging in the following years, during which the surface will be exposed to the climatic conditions of the region. These two types of change can be simulated 195in a laboratory environment; the variations observed on the characteristics of bitumen constitute a valuable indicator of their durability This process is particularly interesting when assessing the benefit achieved by addition of a polymer: the study involves comparing the results obtained on pure bitumen on the one hand and on several modified bitumens on the other, thus eliminating uncertainty as to how far the aging simulated in the laboratory represents actual conditions. The evaporation of the lightest fractions of the bitumen, the chemical change of species present by condensation polymerisation and oxidation on contact with the air and the dete- rioration by ultra-violet rays are all factors that accelerate aging of a binder. Inclusion of a polymer in the bitumen increases its durability and limits or delays the consequences of these phenomena, This improvement can be shown by a wise choice of methods for characterising the bituminous binder, taking into account the presence of the polymer. In certain cases, the polymer can be analysed independently of the bitumen. In order to reveal the benefit contributed by the polymer, two comparative studies were con- ducted, one on anhydrous binders for use in surfacing, the other on emulsions for use in spray- ing. In both cases, the binders were characterised after simulation of aging in several stages. 2. SIMULATION OF AGING ‘Two protocols are applicable for simulating aging of the binder, one for surfacing binders and the other for bitumen emulsions. In the first case, the hardening resulting from processing in the coating plant is simulated by the RTFOT test (Rolling Thin Film Oven Test; EN 12607-1), which involves exposing the binder, in a thin film in cylindrical vials, to a temperature of 163°C for 1 hour 15 minutes During the test, the binder film is constantly renewed by rotating the vial and blowing hot air into the vials accelerates the oxidation process The binder produced in this step can then be used for an aging test through PAV or Pres- sure Aging Vessel (EN 14769), which simulates effect of several years in situ. The binder is exposed for a minimum of 20 hours to a pressure of 2.1 MPa, in an oven at a chosen tem- perature, between 80°C and 115°C In the second case, simulation of aging involves first stoving of the bituminous emulsion in a thin film, for 24 hours at ambient temperature then 24 hours at $0°C, with the thickness of the residual binder film at 1 mm (EN 14895). The binder is then in “recovered” state (simula- tion of short-term aging: a few days after application in situ). The test may also be extended to 24 hours at 85°C, and the binder is then in “stabilised” state (simulation of medium-term aging: 6 months to 1 year in situ). The binder produced by this operation may then be used for aging by PAV (EN 14769) according to the same conditions as for bitumen for surfacing (simulation of long-term aging—several years in situ). ‘At each stage, the binder is sampled and characterised; the change in its characteristics in relation to those of the fresh binder gives us information on its conservation properties. 3. CHARACTERISATION OF BINDERS AND POLYMER, In addition to the values for penetration (EN 1426) and the softening point (EI properties of binders were monitored during this study. 1427), other 3.1 Analyses to assess the binder’s performance Elastic recovery (EN 13398) characterises the binder’s ability to return to its original shape after being deformed; this property tells us about its self-healing capacity and about its fatigue resistance. Pendulum cohesion (EN 13588), suitable particularly for spraying binders, gives informa- tion on the shearing and stripping resistance of aggregates. Characterisation tests according to the Superpave reference system (Asphalt Institute, 1995) were also performed. 196BBR (Bending Beam Rheometer) according to AASHTO T313/EN 14771 is used for characterisation of performance at low temperature. The test involves exposing a beam of bitumen to three-point bending and determining the influence of temperature on the result- ing deflection and the rigidity of the bitumen. This test determines two critical temperatures below which there is risk of cracking for an asphalt mix. ‘The first is the equimodule temperature (temperature at which the bitumen has a stiffness modulus of $ = 300 MPa): when the modulus becomes too high, the binder becomes fragile and is likely to crack. The second is the temperature at which the modulus variation gradient according to the load time (m) is 0.300: a higher gradient is needed to relax the stresses inside the material and reduce the risk of cracking. DTT (Direct Tensile Strength) AASHTO T314: this test characterises the binder’s behav- iour when subjected to stretching at low temperature: it involves determining the temperature at which, during stretching at constant rate, the elongation at break reaches 1%, The suitability of Superpave tests for PMB characterisation has been studied previously (Lecomte et al. 2000, Chappat et al. 2000). 3.2 Analyses for checking the state of the SBS polymer Infrared absorption spectroscopy helps identify the chemical functions present in a sample. In fact, the links between atoms making up a molecule may be considered to be “springs” with specific vibration frequencies and absorb the electromagnetic rays of the corresponding energy. When the molecule is exposed to infrared rays, it absorbs at various frequencies, with each frequency characteristic of a chemical function. In particular, in the case of SBS-modified bitu- men, two characteristic peaks are clearly visible: a peak at 966 cm’! (C-H bond connected to ‘CEC function from the butadiene) and a peak at 700 cm" (aromatic C-H bond of the styrene). These two peaks are usually observed to check the presence of SBS in a modified binder and may also in certain conditions be used for quantity dosing Epi-fluorescent microscopy is carried out as follows: a sample subjected to ultraviolet exci- tation (365 nm) emits radiation in the visible spectrum, when it contains aromatic molecules Given the differences between bitumen and polymer in terms of distribution of the aromatic functions, this is clearly distinct from the bitumen matrix. This technique may therefore be used to observe the morphology of the SBS in a modified binder and check the compatibility of the bitumen and the polymer. Gel permeation chromatography (GPC), also known as Steric exclusion chromatography (SEO), is a technique allowing separation of molecules according to their size. This tech- nique, applied to analysis of polymers in a bitumen matrix, will be described in greater detail ina subsequent paragraph. 4 RESULTS 4.1 Study on anhydrous binders The study on bitumen for hot mixes was conducted on different modified bitumens. A pure bitumen with the same penetration has been taken as a point of comparison. The choice to give all binders in this study equal penetrability (55-60 1/10 mm) elimi- nates uncertainties due to different hardness of bitumens: difference in rheological behaviour between hard bitumen and soft bitumen. The improvement of properties of bitumen binders by adding polymer is already widely aknowledged: it reduces thermal susceptibility, increases the plasticity range and cohesion, and gives a considerable elongation capacity. Generally speaking, long-term aging results in deterioration and transformation which cause the binder to become fragile, which may lead to thermal cracking in the bitumen mix 197Table I. Characteristics of fresh binders Purebitumen C25 C5 CTS Penetration at 25°C 1/10mm_— 53 5660. R&B temperature °C 50,2 SL8 81,0 84,5 Fraass temperature *C 16,7 171 19,1 20,1 BER Tatm=0.300 ce} 18,2 “184-186 -21 TatS=300MPa °C 18,6 “18,8 -19,3 23,6 mat T(S = 300 MPa) 0,295, 0,293 0,289 0,267 DIT Tat l%clongation °C 16,7 194 22,5 25.4 Table 2. Characteristics of aged binders. Purebitumen C25 CS CTS Penetration at 25°C 1/10mm 20 24 838 R&B temperature °C 63,2 663 731 81S Fraass temperature °C 13,2 141-161-182 BBR Tatm=0.300 “c -12,5 “12,8 12,5 -15 fatS=300MPa °C -15 15,2 17,3 19,1 mat S= 300 MPa 0,275 0.275 0,258 0,250 prt Tat elongation °C -15.6 -16 20,7 -21,3 This study was focused on the cold behaviour of binders and the change in this behav- iour during long-term aging. The properties at low temperature of the binders analysed are characterised by the Fraass breaking-point tests and behaviour is characterised by the bend- ing beam rheometer (BBR) and in direct tensile strength testing (DTT). These various tests were performed on three modified bitumens with different SBS con- tents (2.5%, 5% and 7.5%), which we will call C2.5, C5 and C7.5, as well as on a benchmark bitumen (pure bitumen grade 50/70). The characteristics of “fresh” binders are shown in table 1 Note the slight influence of the change on the critical temperatures determined on the bending beam rheometer. This observation turns out consistent with the results obtained from studies performed previously: indeed, the binder’s behaviour is improved only with SBS contents higher than 5% (Corté et al. 199, Asphalt Institute 1995) Afterwards, these binders undergo two successive aging processes: RTFOT (Rolling Thin Film Oven Test - EN 12607-1) and PAV (Pressure Aging Vessel - EN 14769). Following these two aging processes, the binders are characterised again: table 2 shows the results obtained. After RTFOT + PAV aging, the following graphs (figures | to 3) show that the improve- ment of the properties of modified binders due to addition of an SBS-type polymer is still. significant. Indeed, the Fraass breaking temperature as well as the critical equimodule temperature decrease constantly as the polymer rate increases, which is a sign of improved behaviour of bitumen binders at low temperature. The temperature at 1% elongation decreases significantly as the SBS content increases. We find that the temperature at m = 0.300, conveying the ability to relax stresses, is con- stant up to a polymer content of 5% 198In conclusion, although we find a slight reduction in the properties at low temperature of modified binders following RTFOT + PAV aging, modification of bitumen binders by SBS. type elastomers helps preserve binders whose characteristics after aging are better than those of pure bitumen. 4.2. Study on binders recovered from emulsions Various methods are available, in order to recover the binder from an emulsion. According to the technique chosen, the binder properties and rheological behaviour can be noticeably affected (Salomon et al. 2008). Indeed, some techniques are designed for simulation of short- term aging, other ones for medium. or long-term aging. One technique of each kind has been used for this 2nd part of the study, which was conducted on two 160/220 bitumen-based emul- sions: a pure 160/220 bitumen emulsion and a 160/220 bitumen emulsion modified with 2.5% SBS (the polymer is incorporated into the bitumen before emulsification). Table 3 shows the characteristics of binders before emulsification. The first stage involves tracking the change in these characteristics after emulsification of the binders, then simulating aging in successive stages: short term (recovered binder), medium. term (stabilised binder) and long term (binder aged by PAV). Note that during this study, 2. 3}? — be ig . s - By * 13; a 0 2 4 6 8 oO 2 A 6 8 Figure 1, Change in the Fraass point of aged Figure 2. BBR tests: Change in the critical binders as a function of the polymer content. equimodule temperature as a function of the polymer content—aged binders ‘longaion ‘Température at 1% SBS content %) Figure 3. DTT tests: Change in the temperature at 1% of elongation at break as a function of the polymer content—aged binders. Table 3. Initial characteristics of binders. 160/220 pure —_-160/220-+ SBS Penetration at 25°C in 1/10 mm (EN 1426) 187 B37 Softening point R&B in *C (EN 1427) 39.0 418 199160220 160220 Residual penetration (4) 10200 25% 888 Increase in soning pin ©) Figure $. Change in the softening point during aging, in °C compared with the initial value. 14 = @ =Fresh binder 13 a en re © — Recovered binder 21 ‘h = 09 s — — Stabilised binder = os "19 ‘oe g OT 7? ‘S| = Aged binder B 06 Me \ & 93-——# : aA 03 BS : 02 on 0 15 20 25 30 35 40 45 50 55 60 65 ‘Temperature in °C Figure 6. Variation in the cohesion of the SBS-modified binder, as @ function of temperature: change in the curves during aging of the binder. 200Table 4, ‘Temperature interval for which cohesion of the SBS-modified binder is greater than 0.5 Jiem? —evolution during aging. ‘Temperature interval 0.5 Siem? Range Initial binder 23-51 28°C Recovered binder 22-52 30°C Stabilised binder 23.55 32°C Binder aged by PAV 31-30 19°C other aging methods were used to complete the assessment, and other types of emulsions were also considered. The results were published elsewhere (Gueit et al. 2008) The graphs in figures 4 and 5 show the percentage of residual penetrability compared with the initial value and the assessment of the R&B softening points, during aging. It appears that these two tests are not sulficient for checking the maintenance of the modi- fied binder’s performance or for differentiating it from pure bitumen. The SBS-modified binder was thus put through additional tests more suited to its specificity. Elastic recovery was determined at 10°C according to the EN 13398 standard. The value obtained on the initial binder was 61%. Following the recovery stage, elastic recovery reached 76%, and this value was maintained during the stabilisation stage. Following aging by PAY, elasticity could no longer be determined since the specimens broke during stretching, due to the hardening of the binder. Pendulum cohesion was determined for the 4 binders according to the EN 13588 stand- ard, In addition to the graphs in figure 6, showing the variation in cohesion as a function of temperature for each binder, a comparison was made based on the temperature interval on which the binder cohesion was greater than 0.5 J/cm?. The results are given in table 4. By way of comparison, cohesion of the binder recovered from pure bitumen emulsion does not exceed 0.8 J/cm’. The results obtained show that the binder maintains is cohesion properties after short- term (recovery) or medium-term (stabilisation) aging. Following the long-term aging simu- lation stage, the binder maintains its performance in terms of cohesion for temperatures of 35°C and higher. For temperatures below 35°C, the cohesion value decreases sharply due to hardening of the binder; remember that at this degree of aging, elasticity is also affected by hardening of the binder. The conjunction of the results obtained by these two tests therefore calls for further investiga- tion, in the form of tests that produce a more accurate characterisation of the polymer itself. The binders were thus observed via epi-fluorescent UV microscopy. The photos in figure 7 show the structure of the bitumen + polymer mix. The morphology of the polymer did not change significantly during aging, which confirms that the polymer was still present in the binder following the aging by PAV stage. This quality result was combined with a quantity test In this aim, the infrared spectrum was conducted on the binders at successive stages in aging to check whether the reduced performance, initially attributed to hardening of the bitu- men, was also connected to a change in the level of the polymer itself. An example of infrared spectrum is given in figure 8 Since the intensity of peaks at 966 cm” and 700 cnr' was in proportion to the binder’s polymer content, it was determined for the different binders considered. It appears that it changes little during aging, and that finally, the binder aged by PAV (simulation of long-term aging) has an infrared spectrum that is almost identical to that of the initial binder, although the elasticity and pendulum cohesion characteristics show a change in the performance of the binder, suggesting possible deterioration of the polymer. In short, the tests for characterising the binder’s performance reveal the strong impact of the PAY stage (simulation of long-term aging). However, the two tests performed to try to explain this trend by analysing the polymer do not show any significant change. The following theory 201(c) Stabilised binder Figure 7, Epi-fluorescent microscopy—Observation of SBS-modified bitumen at different stages in the aging process. (d) Aged binder SBS-modified bitumen Area of absorption of the polymer Auisuog eondg aia” "aba aon Wave number (cm-1) Figure 8. Detection of presence of SBS in a binder modified by infrared spectrometry characteristic peaks at 966 cm? and 700 cm! may be put forward to explain this phenomenon: deterioration of the SBS occurs by segmen- tation of macro-molecules, but not by their complete destruction. The elementary chemical functions are therefore still detected by infrared absorption spectroscopy, and the length of the molecules remains sufficient for them to be revealed by epi-fluorescent microscopy, In short, 202these two analytical techniques allowed us to check that the polymer was still present in the binder following aging by PAV, but did not give indications as to its state of conservation, To better understand the change in SBS during aging of the binder, it is therefore neces- sary to refine the study using a technique for separating molecules according to their size. gel permeation chromatography. This technique can be used for all types of polymer-modified binders, whether they are anhydrous binders for surfacing or binders recovered from emulsion. 43 Characterisation by gel permeation chromatography GPC, also named “steric exclusion chromatography”, is a technique which consists of separat- ing molecules according to their size, by injecting a solution of the sample through a porous matrix. Largest molecules are not retained and flow freely in the column at the same speed as the solvent (here, tetrahydrofurane), whereas the smallest molecules are retained in the matrix pores. Retention time is inversely proportional to the logarithm of molecular weight. This kind of technique has been previously used for the analysis of pure bitumens (Brilé & Migliori 1983, Briilé et al. 1987) and polymer modified binders (Kraus 1981, Xiaohu & Ulf 2000). Typically, the chromatogram for a PMB comprises two peaks: one for the polymer (high molecular weights) and the second for the bitumen (average and low molecular weights). To understand why there are two peaks that correspond to the bitumen and the polymer, we can give a few orders of magnitude: SBS has an average molecular weight of about 160,000 daltons, whereas that of bitumen is under 1000 daltons. The maximum molecular weight of asphaltenes, the heaviest molecules in bitumen, is around 10,000 daltons. In order to produce a more marked SBS peak to provide a better understanding of how the polymer changes, the results shown here are for a PMB containing 5% polymer instead of 2.5%, Figure (9) displays the results obtained for a PMB at three stages: fresh binder, binder after a “low ageing” thin film method and binder after Pressure Ageing Vessel (“high aging method”). During the aging process, especially in the PAV, the polymer peak corresponding to the highest molecular weights (a) decreases slightly. This tends to confirm that one part of the polymer undergoes a change. Fragmentation of molecules leads to a broadening of the right side of the polymer peak in the area corresponding to medium molecular weight (b). Furthermore, the left side of the bitumen peak (c) is also higher after the ageing process. This is usually Fresh binder f 9 Binder after low ageing method —— Binder after high ageing method (PAV) = siumen | | a Polymer Peak gs Peak = () 2 (@) ° ‘SN i 0.00 5.00 10.00 15.00 20.00 26.00 30.00 35.00 Retention time in minutes Figure 9. Gel permeation chromatography of Polymer Modified Binder. Solvent: tetrahydrofurane, Detection by refractometer. Signal intensity as a function of retention time in minutes. 203explained by an increase in asphaltene content (the heaviest molecules in bitumen), but may also be partly due to the presence of polymer fragments with a molecular mass similar to that of asphaltenes. However, the evolution of the shape of the peak corresponding to SBS throughout binder aging shows that the main part of the polymer remains intact. 5 CONCLUSION ‘These different studies have proven the utility of modifying a bitumen using SBS. We observe improvements in the binder’s performance in many aspects, which can be measured in a laboratory and are tangible on the ground: improvement in mechanical behaviour at low temperature, increase of the softening temperature, addition of elasticity, increase in cohe- sion on broad temperature range. The addition of polymer also has a positive impact on the binder’s durability. This was assessed initially by characterising several binders following their manufacture, then by track- ing the change in their characteristics during successive aging stages (short term, medium. term, long term) simulated in the laboratory. Laboratory assessment of the evolution of polymer efficiency during aging was affected by the hardening of the bitumen: this caused the binder to become rigid at low temperature, leading to decreased performance in terms of elasticity and cohesion. This phenomenon could also be attributed firstly to deterioration of the SBS; to eliminate any uncertainty, additional tests were conducted to assess its state of conservation. The objective was to char- acterise the SBS itself, using a technique to separate it from the bitumen. The gel permeation chromatography analyses showed that most of the polymer had retained its original charac- teristics, particularly in terms of the size of molecules, a property that determines the poly- mer’s effectiveness in the mix, In conclusion, we have been able to show that incorporating a polymer into bitumen improved its mechanical performance in a sustained manner. REFERENCES Asphalt Institute (USA) 1995, Performance Graded asphalt—Binder specification an testing, Asphalt Institute Superpave Series n° Briilé, B. & Migliori, F. 1983, Application de la chromatographic sur gel perméable (GPC) & la cara- ctérisation de bitumes routiers et de leur susceptibilité au vieillissement artificiel, Bulletin de liaison du laboratoire des Ponts et Chaussées, 128, ref 2868. LPC, France. Briilé, B,, Ramond, G. & Such, C. 1987, Relations composition—structure—propriétés des bitumes routiers - Etat des recherches au LCPC, Bulletin de liaison du laboratoire des Ponts et Chaussées, 148, ref 3179. LCPC, France, Chappat, M., Poirier, LE., Robert, M. & Durand, G. 2000. Appréciation & partir des essais SUPER- PAVE et de traction sur liants de impact du vieillissement de liants modifiés vis 4 vis du comporte- ment a froid, RGRA n° 787. Colas, France. Corté, LF et al. 1999, World Road Association (PIARC), Committee 8—Flexible roads, 1999, Use of modified bituminous binders, special bitumens and bitumens with additives in road pavements, LCPC Technical guide, n° 502.714. LCPC, France. Gueit, C., Robert, M. & Durand, G. 2008. Characterisation of the different phases in the life cycle of the binder in @ bitumen emulsion: recovery methods. Zurasphalt Congress, publication n° 405-004. Colas, France. Kraus, G. 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