45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic

METHODS FOR DETERMINATION OF AFFINITY BETWEEN AGGREGATE AND BITUMEN

Dauk Pavol, Hadvinov Marcela, Viovsk Jozef
Slovak University of Technology , Faculty of Chemical and Food Technology , Institute of Organic Chemistry, Catalysis and Petrochemistry , Department of Crude Oil Technology and Petrochemistry,Radlinskho 9, 812 34 Bratislava, Slovakia

Abstract: Methtods for determination of the affinity between aggregate and bitumen apply various ways of aggregates coating, straining conditions and processes of evaluation of bintumen layer on the aggregate surface. The work describes the differences of particular methods and presents advantages of the method EN 12 297-11 Bituminous mixtures. Test methods for hot mix asphalt. Part 11: Determination of the affinity between and bitumen. Key words: Bitumen, aggregate, affinity

INTRODUCTION It is well known that adhesion at the interface between bitumen and aggregate is one of the principal functional properties to guarantee durability of asphalt mixes. But the adhesion can be reduced and the cohesion within asphalt lost through the presence of water at the bitumen/stone interface. The phenomenon is known as stripping. It is known from experience and through experiments that some aggregates possess characteristics that allow very good adhesion. Other stone types on the other hand display bad adhesion. Furthermore, the adhesion is also affected by the properties of the bitumen. Nevertheless, it is known that the origin and properties of the mineral aggregate have a dominant effect compared to the origin of the bitumen [1]. Mostly, the reduced resistance against stripping of a certain aggregate can be improved by adding hydrated lime (or filler containing hydrated lime) to the asphalt mix. The use of additives in the bitumen can also improve the adhesion, but work in general more selectively and depend on the aggregate/bitumen combination. Many methods have been developed and applied to predict the susceptibility of moisture to asphalt mixtures. These methods can be classified into two categories: qualitative tests and quantitative strength tests. The Boiling Water Test [2,3] and Static Immersion Test [3,4] are qualitative tests, while the Lottman Test [5], Tunnicliff and Root [6], Modified Lottman Test [7], Texas Freeze-Thaw Pedestal Test [8] and Immersion-Compresion Test [9] are quantitative strength tests [Roberts, Kandhal, Brown, Lee, Kenedy 1996]. The strength tests allow a numerical comparison to be made between hot mix asphalts (HMA) mixtures. Research of the stripping effect can be further subdivided into three levels of investigation: the micro, meso and macro levels [1].

45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic

On a micro-scale level, Plancher et al [10] looked for components in bitumen, which display a particular ability to adhere to specific components in the aggregate structure. The polarity of these components can explain a strong polar bond. A polar bond is a bond where components with opposite electrical loading/charge attract each other. Normally these types of bonds are very strong. However, these more polar components seem soluble and vulnerable to the polar solvent action of water, which has the effect of removing polar bond. On a meso-scale level, Nsler [11] conducted research into the objective quantification of the remaining percentage of bitumen-coated aggregates after the mix was exposed to miscellaneous humid conditions. Here the emphasis was on avoiding visual determination in favour of analysis employing a photometric method. Furthermore, he quantified the objective adhesion by measuring the loss of the E-Modulus of compacted asphalt samples by using a Nottingham Asphalt Tester (NAT). With this method the same asphalt samples were tested before and after the water treatment. On a macro-scale level, Rand D.A. et al [12] have tried to quantify the effects on functional properties by performing wheel-tracking (or rutting tests) under water. Several aggregate types were investigated, and are able to be categorised in mineral families such as Quartsite, Porphyry, Limestone, Granite, and others. Among these standards the Rolling Bottle Test according to the European Standard [13] is common to sort out good from bad bitumen-aggregate systems. Even though the boundary conditions of the test are specified in detail, the residual degree of bitumen coverage is estimated from visual inspection. This European Standard specifies procedures for the determination of the affinity between aggregate and bitumen and its influence on the susceptibility of the combination to stripping. This property is intended to be of assistance to the designer for mixture design rather than as a type test. Susceptibility to stripping, as determined by these procedures, is an indirect measure of the power of a binder to adhere to various aggregates, or of various binders to adhere to a given aggregate. The procedures can also be used to evaluate the effect of moisture on a given aggregate-binder combination with or without adhesion agents including liquids, such as amines, and fillers, such as hydrated lime or cement. In the rolling bottle method, the affinity is expressed by visual registration of the degree of bitumen coverage on uncompacted bitumen-coated mineral aggregate particles after influence of mechanical stirring action in the presence of water. The rolling bottle test is a simple but subjective test and suitable for routine testing. It is not appropriate for aggregates that are highly abrasive. In the static test method, the affinity is expressed by visual registration of the degree of bitumen coverage on uncompacted bitumen-coated mineral aggregate particles after storage in water. The static test is a simple but subjective test that is less precise generally but can cope with high PSV-aggregates. In the boiling water stripping test method, the affinity is expressed by determining the degree of bitumencoverage on uncompacted bitumen-coated aggregate after immersion in boiling water under specified conditions.

45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic

The boiling water stripping test is an objective test and has a high precision. However, it is a more specialist test because it requires greater skill of the operatives and uses chemicals as reagent. RESULTS Samples of modified bitumen were prepared by mixing of bitumen N4326 with five modificators (4% m/m). Properties of the modified bitumen N4632 are in Table 1. Table 1. Characteristics of bitumen samples Softening point Penetration Break point Sample Bitumen+Modificator RB at 25C Fraass No. [C] [0,1mm] [C] 1 N4632 + SBS-Rubber1 76 88 -15 2 N4632 + SBS-Rubber2 72 94 -21 3 N4632 + Crumb rubber 46 87 -10 4 N4632 + EVA 53 92 -10 5 N4632 + PE 47 86 -12 6 N4632* 44 122 -11 * Bitumen N4632 without modificator, EVA ethylene-vinylacetate, PE polyethylene, SBS styrene-butadiene-styrene copolymer. Bottle rollig test The rolling bottle test according to the European standard [3] was used to evaluate the influence of modificators on the affinity between bitumen N4632 and aggregate Solonica 8/11. The mixing temperature of agregate (510g) and bitumen (16g) was 165C. The mixed material was split into three parts each weighting 150 2g. The first part of the sample was transferred into the bottle with distilled water. The bottle, with glass rod inside, was placed on the roling machine and the rolling procedure was started. The rolling of the bottle at the room temperature was stopped after 6 hours. Three operators carried out a visual determination of the bitumen coverage independently. The whole has been repeated with the two remaining 150g samples. Table 2 Visual determination of area covered by bitumen Sample Operator No. O1 1. 2. 3. 4. 5. 6. 2 1 3 5 4 6 Operator O2 4 1 3 5 2 6 Area Operator = coverage O3 O1+O2+O3 % 1 7 40 2 4 45 5 11 30 4 14 25 3 9 35 6 18 25 Ranking 2 1 4 5 3 6

Surface of the aggregate particles covered by bitumen have been also estimated using a photographic record (example on Figure 1). The Photoshop

45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic

software program was used for the determination of bitumen-covered and free areas of aggregate, the results are shown in Table 3. Table 3. Evaluation of bitumen agregate affinity using a photographic record
Sample No. 1. 2. 3. 4. 5. 6. Pixels corresponding to total area on to covered area on aggregate aggregate 1,244912E+06 5,759480E+05 1,357360E+06 5,060120E+05 1,184856E+06 3,957420E+05 1,314639E+06 3,496940E+05 1,314622E+06 4,009600E+05 1,322527E+06 3,716300E+05 Area covered by bitumen [%] 46,3% 37,3% 33,4% 26,6% 30,5% 28,1% Ranking 1 2 3 6 4 5

Figure 1. Sample 4 after the rolling test After the visual and photographic mesurements the samples were extracted by toluene. The amount of the extracted bitumen was used for a further estimation of the area of the aggregate covered by bitumen (see Table 4). Table 4. Evaluation of the bitumen agregate affinity by the toluene extraction Weight [g] Bitumen Agregate Sample Covered Extracted extract after test No. Covered Bitumen agregate bitumen after test Ranking agregate and after after test after test % m/m extraction 1 159,675 4,852 159,509 155,558 3,951 81 2 2 164,630 5,003 164,482 160,234 4,248 85 1 3 155,980 4,735 155,651 152,306 3,344 71 4 4 159,427 4,846 159,317 156,055 3,262 67 5 5 156,793 4,727 155,397 151,973 3,424 72 3 6 156,793 4,760 156,475 153,567 2,908 61 6

45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic

The Boiling Water Test First step of this test [3] is a 10 minutes bath of a 200g of aggregate sample covered with bitumen in boiling water. Afterwards the aggregate sample stays in contact for five minutes with hydrochloric acid of a given concentration and amount. Finally, the acidometric titration is used for the estimation of volume of the hydrochloric acid consumed by the reaction with the free surface of the aggregate. The dependence of the free area on the consumption of the hydrochloric acid for 200g of aggregate - bitumen system is shown on Figure 2.
120 S (% Area not covered) 100 80 60 40 20 0 0,00 1,00 2,00 3,00 4,00 5,00 y = 0,7015x2 + 19,145x - 3,7766 R 2 = 0,9965

V [ml - 0,1M HCl]

Figure 2. Calibration curve of the free area for 200g of aggregate S (% Area not covered) = f(V ml - 0,1HCl ) Table 5. Results of the Boiling Water Test of the bitumen aggregate affinity using the calibration curve shown in Figure 2 0,1M HCl Area Ranking Consumption Sample No. free covered [ml] 1 2,70 48 52 3 2 3,03 55 45 4 3 3,13 57 43 5 4 2,51 45 55 2 5 2,38 42 58 1 6 3,83 70 30 6 CONCLUSIONS The EN 12697-11 : 2005 standard specifies procedures for the determination of the affinity between aggregate and bitumen and/or the susceptibility to stripping. This procedures are intended to be of assistance for the aggregate bitumen - modificator mixture design rather than a type test. Susceptibility to stripping, as determined by these procedures, is an indirect measure of the power of a binder to adhere to various aggregates, or of various binders to

45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic

adhere to a given aggregate. The procedures can also be used to evaluate the effect of moisture on a given aggregate-binder combination with or without adhesion agents including liquids, such as amines and fillers, such as hydrated lime or cement. The bottle rolling test is based on a relatively long lasting (6 - 24 hours) mechanical stress of the sample (aggregate coated with bitumen) in water of temperature 20 - 25 C. The evaluation of the free area of the aggregate has yield good agreement between the visual and photographic methods, though both methods rely only on the analysis of one surface of the sampled aggregate. Furthermore, the visual approach is biased with the subjective judgments of the operators. Regardless of the mentioned drawbacks the best results were obtained for the SBS modificators in the bottle rolling test. In addition, the extraction of the remaining bitumens from the aggregate samples after the bottle rolling test has shown that only a small part of bitumen is removed from aggregate during the test. Rather the extratcion indicates that bitumen on the surface of the aggregate changes the shape (collaguates) and thus covers a smaller surface. This is why the amounts of bitumen obtained by the extraction do not correlate with the bitumen covered surface which were determined by the visual and/or photographic methods. The boiling water test is focused on a high temperature (100 C) - short period (10 minutes) stress of the sample. The titration method has been used to analyze the area of aggregate covered by bitumen. The EVA modificator has yield the best results (smallest free area of the aggregate) in the case of the boiling water test. It is noteworthy that the titration methods is unbiased, by means of the subjective judgment of an operator and the entire surface of the aggregate is analyzed, what are quite interesting advantages in comparison to the visual or photographic methods. The titration method could be also employed for the evaluation of the aggregate free surface in the bottle rolling test. Nevertheless, the titration method is not mentioned within the EN 1269711 : 2005 standard, in which case the visual estimation is preferred. REFERENCIES [1] Hunter E. R., Ksaibati K.: Evaluating moisture susceptibility of asphalt mixes, 2002, http://www.mountain-plains.org/pubs/pdf/MPC02-138.pdf [2] ASTM D3625 - 96(2005) Standard Practice for Effect of Water on Bituminous-Coated Aggregate Using Boiling Water [3] EN 12697-11:2005 Bituminous mixtures - Test methods for hot mix asphalt - Part 11: Determination of the affinity between aggregate and bitumen [4] American Association of State Highway and Transportation Officials, AASHTO T 182: Standard Method of Test for Coating and Stripping of Bitumen-Aggregate Mixtures 1984 [5] ASTM D4867/MN DOT MODIFIED Revised 2/19/99: Standard Test for Effect of Moisture on Asphalt Concrete Paving Mixtures [6] ASTM D4867 / D4867M - 09 Standard Test Method for Effect of Moisture on Asphalt Concrete Paving Mixtures [7] American Association of State Highway and Transportation Officials: AASHTO T 283: Standard Method of Test for Resistance of Compacted Hot Mix Asphalt (HMA) to Moisture-Induced Damage, 2007

45th International Petroleum Conference, June 13, 2011, Bratislava, Slovak Republic

[8] Kennedy T.W.: Texas freeze-thaw pedestal test for evaluating moisture susceptibility for asphalt mixtures Volume 253: 1982 [9] American Association of State Highway and Transportation Officials: AASHTO T 165: Standard Method of Test for Effect of Water on Compressive Strength of Compacted Bituminous Mixtures, 2002 [10] Plancher I. H., Dorrence S.M, Petersen J.C.:Identification of Chemical types in asphalts strongly adsorbed at the asphalt aggregate interface and their relative displacement by water, AAPT, p. 151, vol 46, 1977. [11] Nsler I.: A Contribution to the Objective and Quantitative Measurement of the Adhesion between Aggregates and Bitumen, Thesis Work, 1999, University of Wuppertal, Institute of Road Construction. [12] Rand D. A.: HMA Moisture Sensitivity, Past, Present & Future, TxDOT Experiences, Paper presented in Session 3, Field Observations and Validation, Designed Tests and Forensic Analysis, Moisture Damage Symposium, Petersen Asphalt Research Conference, 39th Annual Meeting, Laramie, Wyoming, July 15-17, 2002. ACKNOWLEDGEMENT The Slovak Research and Development Agency supported this work under contract No. APVV-20-0367705.