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Investigation the self-healing mechanism of aged bitumen using microcapsules containing rejuvenator
Construction and Building Materials 85 (2015) 49–56
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Construction and Building Materials journal homepage: www.elsevier.com/locate/conbuildmat
Investigation the self-healing mechanism of aged bitumen using microcapsules containing rejuvenator Jun-Feng Su a,⇑, Erik Schlangen b, Ying-Yuan Wang a a b
Department of Polymer Materials, School of Material Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, China Department of Materials and Environment, Faculty of Civil Engineering & Geosciences, Delft University of Technology, 2628CN Delft, The Netherlands
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
The microcapsules containing
The capillarity behaviors of rejuvenator in self-healing bitumen by microcapsules, (a–c) a microcrack was generated by liquid N2 with the width about 10–15 lm, the microcrack propagates and pierce the shells of microcapsules, (d and e) the liquid of rejuvenator leaked out from microcapsules and flowed into the microcapsules, and (f) movement trace and direction of rejuvenator during the capillarity.
rejuvenator can be broken by microcracks. With the help of capillarity, the rejuvenator can fill the microcracks. With the help of the penetration of rejuvenator, the aged bitumen has a trance to recovery its virgin properties.
a r t i c l e
i n f o
Article history: Received 4 June 2014 Received in revised form 10 January 2015 Accepted 21 March 2015 Available online 31 March 2015 Keywords: Bitumen Self-healing Rejuvenator Microcapsules
a b s t r a c t The aim of this paper is to investigate the self-healing mechanism of aged bitumen using microcapsules containing rejuvenator. Various microcapsule samples were successfully fabricated and the mean size and shell thickness were adjusted. It was found that the shell thickness was not greatly affected by the core/shell ratios and the emulsion stirring rates. These microcapsules can survive in melting bitumen with a good thermal stability. Based on these data, a typical microcapsule sample, fabricated by 3000 r min1 with core/shell ratio of 2/1, was selected to investigate the self-healing mechanism. The whole self-healing process was observed including the crack generation, capillarity and the diffusion behaviors. The results showed that microcapsules broke by microcracks and leaked the oily–liquid rejuvenator into microcracks. With the help of capillarity, the rejuvenator filled the cracks with a movement speed mainly determined by the volume of microcapsules in bitumen. A diffusion phenomenon was also observed by using a fluorescence microscope. Properties of virgin and rejuvenated bitumen measurements confirmed that the aged bitumen can be partly recovered by the microcapsules containing rejuvenator. Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction ⇑ Corresponding author. Tel./fax: +86 22 26210595. E-mail addresses: [email protected], [email protected] (J.-F. Su). http://dx.doi.org/10.1016/j.conbuildmat.2015.03.088 0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
Every year about 95% of the almost 100 million tonnes of bitumen is applied in the paving industry where they essentially act
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as a binder for mineral aggregates to form asphalt [1]. One important issue need to be considered is the ageing of bitumen from climate and traffic in service life [2]. After years of usage, the stiffness of asphalt concrete increases while its relaxation capacity decreases, the binder becomes more brittle causing development of microcracks and ultimately cracking of the interface between aggregates and binder occurs [3]. The ageing problem of bitumen leads to pavement failure including surface raveling and reflective cracking. It will increase the expense of maintaining bituminous pavements [4]. Although part of aged asphalt can be recycled as an economic and environmentally sound solution, it is still a big problem to deal with the hazardous material of aged asphalt in large quantities. Therefore, preservation and renovation bitumen of pavement is a low-cost and effective approach. An increase in the application of a higher percentage of the preservation and renovation of asphalt pavement is achievable using a rejuvenator. It is the only one method that can restore the original properties of the pavements [5]. The most important goal of utilizing rejuvenator products is to restore the asphaltenes/maltenes ratio. Rejuvenating agents have the capability of reconstituting the binder’s chemical composition and consist of lubricating and extender oils containing a high proportion of maltene constituents [6]. However, a rejuvenator is not successfully applied because it is hard to penetrate the pavement surface. Shen et al. [7] reported the results of using three rejuvenators. It was found that none could penetrate into the asphalt concrete more than 2 cm. When applying these materials, the road must be closed for some time after their application. The rejuvenator, at the same time, will cause a high reduction of surface friction of pavement for vehicles. Moreover, an important aspect of these rejuvenators is that they may be dangerous to the environment. Encapsulation rejuvenator inside-usage in asphalt may be an alternative approach. García et al. [8] reported a method to prepare capsules containing rejuvenator by using epoxy resin as coating and pours sand as skeleton. We reported a method to fabricate microcapsules containing rejuvenator utilizing methanol modified melamine–formaldehyde (MMF) resin as shell material [9]. These microcapsules had satisfactory thermal stability in bitumen and reliable mechanical properties resisting the mixing process and temperature changes [10]. It had been proved that this product was environmental-friendly powder encapsulating suitable size rejuvenator for chemical engineering and construction engineering [11]. Self-healing materials based on microcapsules have been studied widely which have structurally incorporated ability to repair damage caused by mechanical usage over time. Monomer is encapsulated and embedded within the matrix materials. When the crack gets to the microcapsule, the capsule breaks and the monomer bleeds into the crack, where it can polymerize and mend the crack [12]. Besides the similar structure of microcapsules self-healing materials for bitumen/microcapsules materials, we still need to consider their special self-healing mechanism. Microcapsules in bitumen can be broken by microcracks, then the released rejuvenator seals the microcracks and permeate surrounding bitumen. The capillaries and penetration behavior will determine the self-healing efficiency of aged bitumen [13]. With the help of capillarity, rejuvenator flows into narrow microcracks without the assistance of, and in opposition to, external forces. Firstly, the core–shell structure of microcapsules is taken into account for the specific requirement such as size distribution, encapsulation ratios and non-biodegradable property, since this influences their service performance. As bitumen acts as thin layers between aggregates which are usually less than 50 lm, size of microcapsules containing rejuvenators should be smaller than 50 lm to avoid being squeezed or pulverized during asphalt forming. Secondly, the shell thickness must be controlled to make sure that the microcapsules have excellent thermal stability. It was reported have found that
thicker shell will enhance the mechanical properties of microcapsules, the microcracks may not able to break these microcapsules [14]. It must be prevented that the microcracks propagation will go round the shells. In view of the above, the aim of this paper is to investigate the self-healing mechanism of aged bitumen using microcapsules containing rejuvenator. Various microcapsule samples were fabricated to optimize the core–shell structures. In order to observe the selfhealing behaviors, liquid nitrogen was used to generate microcracks in aged bitumen. The effects of mean size and shell thickness of microcapsules were evaluated to understand the self-healing behaviors. At the same time, the capillaring and penetration behaviors were analyzed to evaluate the rejuvenator movement. Properties of virgin and rejuvenated bitumen were compared to evaluate of recovery for aged bitumen. 2. Experimental 2.1. Materials The shell material was commercial prepolymer of melamine–formaldehyde modified by methanol (solid content was 78.0%) purchased from Aonisite Chemical Trade Co., Ltd. (Tianjin, China). The core material used as rejuvenator is dense, aromatic oil (density is 0.922 g/cm3, viscosity is 4.33 Pa s) obtained from Petro plus Refining Antwerp (800DLA, Belgium). Styrene maleic anhydride (SMA) copolymer (ScripsetÒ 520, Hercules, USA) was applied as dispersant. A small percentage of the anhydride groups have been established with a low molecular weight alcohol and it is fine, off-white, free flowing powder with a faint, aromatic odor [15]. The bitumen used in this study was 80/100 penetration grade obtained from Kuwait Petroleum. The aged bitumen 40/50 penetration grade was artificially produced by thin film oven test. The 40/50 aged bitumen was then blended with microcapsules using a propeller mixer for 30 min at 160 °C with a constant speed of 200 r min1. 2.2. Microencapsulation procedure The method of fabrication microcapsules containing rejuvenator by coacervation proceed can be divided into three steps [16]: (1) SMA (10.0 g) was added to 100 ml water at 50 °C and allowed mix for 2 h. Then a solution of NaOH (10%) was added dropwise adjusting its pH value to 10. The above surfactant solution and rejuvenator were emulsified mechanically under a vigorous stirring rate for 10 min using a high-speed disperse machine. (2) The encapsulation was carried out in a 500 ml three-neck round-bottomed flask equipped with a condensator and a tetrafluoroethylene mechanical stirrer. The above emulsion was transferred in the bottle, which was dipped in a steady temperature flume (room temperature). Half of MMF prepolymer (16 g) was added dropwise with a stirring speed of 500 r min1. After 1 h, the temperature was increased to 60 °C with a rate of 2 °C min1. Then another half of prepolymer (16 g) was dropped in a bottle at the same dropping rate. (3) The temperature was increased to 75 °C. After polymerization for 1 h, the temperature was decreased slowly at a rate of 2 °C min1 to ambient temperature. At last, the resultant microcapsules were filtered and washed with pure water and dried in a vacuum oven. 2.3. Morphologies observation An optical microscope (BX41-12P02, OLYMPUS) was used to check the fabrication process of microcapsules in emulsion. About 1 ml of the colloidal solution was extracted and spread on a clean glass slide (1 3 cm). The dried microcapsules were adhered on a double-side adhesive tape without cracking the shells. The surface morphologies were observed by using an Environmental Scan Electron Microscopy (ESEM, Philips XL30) at an accelerated voltage of 20 kV. 2.4. Mean size and shell thickness of microcapsules The mean size of microcapsules was measured by a laser particle size analyzer (HELOS-GRADIS, SYMPATEC GMBH, Germany). About 2 g microcapsules was mixed in 5 g epoxy resin. After the composite was dried at room temperature, it was carefully cut to obtain the cross-section. The thickness of shells can be measured from the ESEM images of cross-section of microcapsules [17]. At least 20 shells of each microcapsule sample were measured and the average data were calculated. 2.5. Thermogravimetric analysis (TGA) The thermal stability characterization of microcapsules was performed on a Dupont SDT-2960 Thermogravimetric analysis (TGA) at a scanning rate of 5 °C min1 in a flow of 40 ml min1 nitrogen (N2).
J.-F. Su et al. / Construction and Building Materials 85 (2015) 49–56 2.6. Microcracks generation in aged bitumen A thin bitumen/microcapsules sample was adhered on a glass sheet. It was carefully poured with a drop of liquid nitrogen (N2) at one end. Microcracks were quickly generated in this sample because of the low temperature brittleness. 2.7. Observation of rejuvenator movement in bitumen Capillarity and diffusion behaviors of rejuvenator in aged bitumen were observed by a fluorescence microscope (CKX41-F32FL, OLYMPUS) using the light characters such as reflection, diffraction and refraction. The scale of fluorescence microscope was applied to measure the size of capillarity and diffusion. As bitumen is a temperature-sensitive material, the observation is in an environment of 0 °C temperature. 2.8. Characterization of virgin and rejuvenated bitumen The properties of virgin bitumen, aged bitumen and rejuvenated bitumen were tested including penetration (ASTM D5), softening point (ASTM D36) and viscosity (ASTM D4402). To simply the research, it was assumed that the rejuvenator in microcapsules had totally been consumed during rejuvenation. The encapsulated rejuvenator in this study is yellow oil without solubility in water. At the end of the fabrication, the un-encapsulated rejuvenator is floating on the surface of emulsion. It was absorbed out using a syringe. Encapsulation efficiency (E) of rejuvenator was calculated by Eq. (1),
E¼
W1 W2 100% W1
ð1Þ
where W1 is the original weight of rejuvenator and W2 is the residue weight of rejuvenator.
3. Results and discussion
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rejuvenator dispersed by ESEM under a 3000 r min1 emulsion rate. It was observed that the organic core material is dispersed into particles in water. After being encapsulated by shell material as showed in Fig. 1(b), the microcapsules are ultimately separated through the regulation of hydrolyzed SMA molecules with core/ shell ratio of 2/1. Fig. 1(c) shows the final dried microcapsules with regular globe shape with smooth surfaces. The mean size is an important parameter for microcapsules containing rejuvenator influencing their application possibility in asphalt. Too tiny size will limit the encapsulated content of rejuvenator. In another case, large microcapsules may be broken in mixing with asphalt concrete. Fig. 2 shows the ESEM morphologies of microcapsules (core/shell ratio of 3/1) with different mean sizes fabricated under emulsion stirring rates of 1000, 2000 and 3000 r min1. It can be seen that the mean sizes decreased sharply with the decreasing of stirring rates because higher stirring rates will smash the oily rejuvenator into smaller droplets. The rejuvenator applied in this study as core material still obeys this rule. Fig. 3 shows shell thickness data of microcapsules. The results suggest that the shell thickness is not greatly influenced by the stirring rates. As the formation of a shell is a coacervation process, the shell thickness is dominated by the amount of shell material. Less core/ shell ratio leads to a higher shell thickness value. It can be concluded that the core/shell ratios nearly do not affect the average size of microcapsules. In other words, the mean size is primarily decided by the core material disperse speed. Therefore, a typical microcapsule sample (fabricated with 3000 r min1 and core/sell ratio of 2/1) was applied to investigate the self-healing mechanism of aged bitumen.
3.1. Characterization of microcapsules containing rejuvenator 3.2. Thermal analysis of microcapsules SMA was applied as a nonionic dispersant by in situ polymerization method in this study. SMA molecules can hydrolyze in water by NaOH and form carboxyl (–COOH) groups. These hydrophilic polar groups, alternatively arranging along the SMA backbone chains, thus associate with water molecules and trimly cover the oil droplets surface with hydrophobic groups oriented into oil droplets and hydrophilic groups out of oil droplets [18]. Optical microphotographs of microcapsules were taken to illuminate the encapsulation details. Fig. 1(a) shows the morphology of
TGA has been extensively applied to investigate the encapsulation effect and shell compactness of microcapsules [10]. The microcapsule sample was composted with increasing temperature according to present residual weight (wt.%). It has been reported in our previous work that this rejuvenator has a marked weight loss between 337 °C and 469 °C owing to the evaporation of oil substance under elevated temperature. Fig. 4(a) shows the typical TGA curve of microcapsule sample fabricated with emulsion rate
Fig. 1. Optical morphologies of microcapsules containing rejuvenator fabrication process, (a) rejuvenator dispersed by ESEM under a 3000 r min1 emulsion stirring rate, (b) microcapsules with core/shell ratio of 2/1, and (c) dried microcapsules with regular globe shape with smooth surfaces.
Fig. 2. ESEM morphologies of microcapsules containing rejuvenator fabricated under emulsion rates of: (a) 1000 r min1 (b) 2000 r min1 and (c) 3000 r min1.
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3.3. Capillarity behaviors of rejuvenator in microcracks
Fig. 3. Shell thicknesses of microcapsules fabricated under various stirring rates.
In order to figure out more details of microcracks generation and the capillarity behaviors of rejuvenator, a bitumen/microcapsules composite (5/95, w/w) was observed continuously by a fluorescence microscope under temperature of 0 °C. The microcapsules were fabricated under core material stirring rate of 3000 r min1 with core/shell ratio of 2/1. As show in Fig. 6(a–c), a microcrack was generated by liquid N2 with a width about 10–15 lm. It propagated successfully and pierced the shells of microcapsules. We can distinguish between rejuvenator and bitumen from the morphology colors of fluorescence microscope, rejuvenator is green and bitumen is yellow. As can be seen in Fig. 6(d and e), liquid rejuvenator leaks out from microcapsules and flows into the microcrack. During a period of time, rejuvenator fills the microcrack and then spread the whole microcrack through capillarity. Especially in Fig. 6(f), we can clearly recognize the movement traces and direction of rejuvenator during the capillarity. To confirm the existence of the capillarity, we compared the states of microcrack in 60 min under 0 °C. Fig. 7(a) shows the original state of a microcrack in bitumen/microcapsules sample with a width of 20 lm. The crack was an arc curve in the sample. Interestingly, the crack is green color after 60 min (Fig. 7b) because it has been filled with rejuvenator coming out from broken microcapsules. Besides the confirmation of the capillarity, we also want to evaluate the extent and rate of rejuvenator through capillarity in microcracks. It is well known that the height L of a liquid column of capillarity is given by Eq. (2),
L¼
Fig. 4. Thermal stability of microcapsules, (a) the TGA plot of pure rejuvenator, (b– d) ESEM morphologies of microcapsules under various temperatures.
of 3000 r min1 and core/shell ratio of 2/1. The TGA curve may reflect thermal stability and structure of polymeric shell. Fig. 4(b and c) show ESEM morphologies of microcapsules under temperatures of 100 °C, 300 °C and 400 °C. It can be seen that the microcapsules still keep the global shape under 300 °C without break. Nearly about 10% weight is lost less than 100 °C for all microcapsule samples because of the evaporation of water and small molecules. The decomposite temperature is at about 396 °C (Fig. 4(d)). This degradation temperature is higher than the melting temperature of bitumen at 180 °C. It indicates the cured MMF resin will not be thermal decomposed mixing with melting asphalt. With the temperature increasing, the shell will firstly crack or broken under high temperature before decomposition. To verify the thermal stability of microcapsules in bitumen, the microcapsules were mixed with melting bitumen under various temperatures for 30 min. Then the shape of microcapsules was observed by an optical microscope. The microcapsules had an average size about 16 lm fabricated under core material stirring rate of 3000 r min1 (core/shell ratio of 2/1). In Fig. 5(a), it can be seen that microcapsules survived in bitumen under temperature 140 °C. With the increasing of temperature to 160 °C (Fig. 5b), 180 °C (Fig. 5c) and 200 °C (Fig. 5d), the microcapsules still kept their global shape without crack and thermal decomposition. These results indicate that microcapsules can resist the thermal effect of bitumen in application.
2c cos h qgr
ð2Þ
where c is the liquid–air surface tension, h is the contact angle, q is the density of liquid, g is local gravitational field strength, and r is radius of tube (crack). However, this rule cannot guide capillarity in self-healing bitumen. Because the microcapsules were homogeneously distributed in bitumen, the rejuvenator could quickly disperse from both sides of a crack. Therefore, we pay more attestation to the time (t) that rejuvenator can finally fill the whole microcrack. When a dry porous material such as a brick or a paper, is brought into contact with a liquid, it will start absorbing the liquid at a rate which decreases over time. For a bar of material with cross-sectional area A that is wetted on one end, the cumulative volume V of absorbed liquid after a time t is,
pffiffi V ¼ AS t
ð3Þ
where S is the sorptivity of the material. As rejuvenator is oily liquid, it may take a longer time for it to disperse due to its high viscosity. Another issue needs to be considered is the volume of microcapsules in bitumen. With higher volume ratio of microcapsules (Vm), the microcrack will, at the same time, have a higher probability to meet microcapsules. Summary of the above-mentioned laws, it can be drawn a conclusion that the capillarity time (T) for microcapsules self-healing material is determined by three aspects including the properties of liquid (M, related to viscosity and contact angle), the volume of cracks (V0 , related to width and length) and the volume ratios of microcapsules in medium. T can be written as an equation,
T ¼ f ðM; V 0 ; V m Þ
ð4Þ
To simplify this complex problem, bitumen/microcapsules samples were prepared with various Vm values to measure the capillarity speeds of rejuvenator. The movement time of rejuvenator is measured to determine the speed of the capillarity using the scale of fluorescence microscope. We investigated both the speeds of the lateral-movement (Fig. 8a) and longitudinal-movement (Fig. 8b) in microcracks under
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Fig. 5. Optical morphologies of microcapsules in melting bitumen under different temperatures for 30 min.
Fig. 6. The capillarity behaviors of rejuvenator in self-healing bitumen by microcapsules, (a–c) a microcrack was generated by liquid N2 with the width about 10–15 lm, the microcrack propagates and pierce the shells of microcapsules, (d and e) the liquid of rejuvenator leaked out from microcapsules and flowed into the microcapsules, and (f) movement trace and direction of rejuvenator during the capillarity.
temperature of 0 °C. The width and length data in Fig. 8 were measured by a fluorescence microscope with scale. In Fig. 8(a and b), the arrows point the directions and tracks of rejuvenator movement. Fig. 8c shows the relationship between the lateral-movement time and the volume of microcapsules (5, 10, 15, 25 and 30 vol.%) in microcracks (width 10, 20 and 30 lm), respectively. The time data were carefully recorded by observing the rejuvenator movements under a fluorescence microscope with a scale. Firstly, it can be known that rejuvenator need more time to complete a lateralmovement in wider microcracks. For example, the times are 67, 54, and 46 min for samples with 5 vol.% microcapsules in microcracks with width of 30, 20 and 10 lm. Secondly, higher volume ratio of microcapsules leads the rejuvenator to take less time for a lateralmovement. The reason may be that more rejuvenator has released out into microcracks and the releasing area is improved. Fig. 8(d)
shows the relationship between the longitudinal-movement time and the volume of microcapsules (5, 10, 15, 25 and 30 vol.%) in microcracks (length 100, 200, 300 lm), respectively. Higher volume ratio of microcapsules also leads the rejuvenator need less time to complete a longitudinal-movement. At the same time, it has been seen that a longer microcrack make the rejuvenator need more time to complete a long-distance movement. However, higher volume ratio of microcapsules (>25 vol.%) will weaken this trend. We can attribute this phenomenon to the mass increasing of rejuvenator in a microcrack. 3.4. Observation of rejuvenator diffusion in aged bitumen Mass transfer by molecular diffusion is one of the basic mechanisms in many branches of science. Molecular diffusion is a
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Fig. 7. Fluorescence microscope morphologies capillarity behavior of rejuvenator in a microcrack, the states of a microcrack in bitumen/microcapsules sample with a width of 20 lm before (a) and after (b) 60 min, the microcrack has been filled with rejuvenator out of microcapsules.
Fig. 8. The capillarity speeds of rejuvenator in bitumen microcracks under temperature of 0 °C, (a and b) the illustrations of the lateral-movement and longitudinalmovement, (c) the relationship between the lateral-movement time and the volume of microcapsules (5, 10, 15, 25 and 30 vol.%) in microcracks (width 10, 20 and 30 lm), and (d) the relationship between the longitudinal-movement time and the volume of microcapsules (5, 10, 15, 25 and 30 vol.%) in microcracks (length 100, 200, 300 lm).
transport property which monitors the rate of mass transfer of species in a medium [19]. In addition, it was reported that the diffusion behaviors of bitumen has great relationship with temperature, viscosity of the diffusion medium, diffusant size and polarity [20]. In this study, we only observe the diffusion processes in order to design and plan microcapsules based bitumen recovery processes, because it is required for determining the rate of mass transfer between the rejuvenator and aged bitumen at given conditions. The diffusion coefficient between liquid–solid phases is mainly determined by liquid molecular structure, solid structure, temperature and pressure. Fig. 9 shows the fluorescence microscope morphologies of rejuvenator leaked out from microcapsules diffusion in aged bitumen at 0 °C for 24 h. A microcrack was generated in this aged bitumen sample previously. It can be
confirmed in Fig. 9(a) that the microcapsules were broken by the microcrack and the rejuvenator flowed out. The diffusion areas were also observed after a period of 24 h. Interestingly, we even can identify the diffusion direction of rejuvenator coming outing of a microcapsule into the aged bitumen as seen in Fig. 9(b). A gradient diffusion layer exists between the rejuvenator and the matrix. Normally, diffusion behavior of binary materials is reflected in its phase diagram. The composition of the phases is dependent on the phase-structures and the temperature, the phase-structures being the border between the one- and twophase regions. Therefore, it can be concluded that various conditions including the aging degree of bitumen and the diffusion temperature. The diffusion coefficient will be discussed in our subsequent research.
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Fig. 9. Fluorescence microscope morphologies of rejuvenator diffusion in aged bitumen at room temperature for 24 h.
Table 1 Properties of virgin and rejuvenated bitumen (penetration value, softing point value, viscosity value).
Penetration (d-mm, 25 °C) Softening point (°C) Viscosity (135 °C) (mPa s)
Original Bitumen (80/100)
Aged bitumen (40/50)
86 46.7 325
43 53.5 578
3.5. Properties of virgin and rejuvenated bitumen In addition to an analysis of rejuvenator diffusion, we wished to evaluate the results of rejuvenating aged bitumen. Efficiency of the rejuvenator depends on its viscosity and the quantity added to the aged bitumen and thus we decided to conduct a preliminary investigation to explore the effects of blending known quantities of rejuvenator with penetration grade bitumen on binder rheology. To this purpose, a series of microcapsules/bitumen samples were first heated at 200 °C for 12 h and then stored for 60 days. The microcapsules applied in this test had an encapsulation ratio of 85% with an average size of approximately 20 lm and had been fabricated under conditions of stirring rate of 3000 r min1 and core/ shell ratio of 1/2. Based on the previous investigation results, it was predicted that the majority of the encapsulated rejuvenator would leak out of the spheres and penetrate into the aged bitumen. The subsequent rejuvenating effect was assessed by comparing the properties of aged bitumen samples under the same conditions. In this study, the original bitumen (80/100) was found to have penetration, softening point and viscosity values of 86 d-mm, 46.7 °C and 325 mPa s. In contrast, the aged bitumen (40/50) had values of 43 d-mm, 53.5 °C and 578 mPa s. The aged bitumen was subsequently rejuvenated with microcapsules at 2–10% by weight of bitumen. Table 1 lists the penetration, softening point and viscosity of the aged bitumen before and after rejuvenation with varying amounts of microcapsules. These data demonstrate that the penetration value increased as the amount of microcapsules In the aged bitumen increased. This result is attributed to a reduction in the ratio of asphaltenes to maltenes. The addition of approximately 10% microcapsules returns the aged 40/50 bitumen to a condition similar to that of the original bitumen. Additionally,
Rejuvenated aged bitumen with microcapsules (wt.%) 2
4
6
8
10
12
50 51.0 573
63 50.3 552
64 49.2 500
70 47.1 470
76 46.6 406
80 45.4 390
the softening point value decreased with the addition of microcapsules. In the aged bitumen, increases in the level of high molecular weight asphaltenes tend to produce a harder material with lower temperature susceptibility and thus increase the softening point. The addition of the rejuvenator, however, is evidently capable of mitigating this effect. Lastly, although the aged bitumen had a high viscosity value, the addition of 10% microcapsules returned the viscosity to 390 mPa s. Therefore the same workability is expected from the rejuvenated bitumen.
4. Conclusions The self-healing mechanism of aged bitumen using microcapsules containing rejuvenator was investigated. The effects of mean size and shell thickness of microcapsules were evaluated for selfhealing behaviors and capillaries and penetration behaviors were analyzed to evaluate the rejuvenator movements. From the mentioned preliminary results, the following conclusions can be drawn, (1) The shell thickness of microcapsules was not greatly affected by the core/shell ratios and the emulsion stirring rates. These microcapsules can survive in melting bitumen with a good thermal stability. This result means that the microcapsules can practically be applied in bitumen without broke before usage. (2) The microcapsules can be broken by microcracks and leaked the oily-liquid rejuvenator into microcracks. With the help of capillarity, the rejuvenator filled the cracks with a movement speed mainly determined by the volume of microcapsules in bitumen.
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(3) Higher volume ratio of microcapsules leads the rejuvenator need less time to complete a longitudinal-movement. (4) With the help of the penetration of rejuvenator, the aged bitumen has a trance to recovery its virgin properties.
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[9] Su JF, Schlangen E. Synthesis and physicochemical properties of novel high compact microcapsules containing rejuvenator applied in asphalt. Chem Eng J 2012;198–199:289–300. [10] Su JF, Qiu J, Schlangen E. Stability investigation of self-healing microcapsules containing rejuvenator for bitumen. Polym Degrad Stab 2013;98:1205–15. [11] Su JF, Schlangen E, Qiu J. Design and construction of methylation-melamineformaldehyde microcapsules containing rejuvenator for asphalt. Powder Technol 2013;235:563–71. [12] Yuan YC, Yin T, Rong MZ, Zhangm MQ. Self healing in polymers and polymer composites. Concepts, realization and outlook: a review. Express Polym Lett 2008;2:238–50. [13] Garcia A. Self-healing of open cracks in asphalt mastic. Fuel 2011;93:264–72. [14] Su JF, Wang XY, Dong H. Micromechanical properties of melamineformaldehyde microcapsules by nanoindentation: effect of size and shell thickness. Mater Lett 2012;89:1–4. [15] Su JF, Wang LX, Ren L, Huang Z. Mechanical properties and thermal stability of double-shell thermal energy storage microcapsules. J Appl Polym Sci 2007;103:1295–302. [16] Su JF, Wang LX, Ren L. Synthesis of polyurethane microPCMs containing noctadecane by interfacial polycondensation: influence of styrene-maleic anhydride as a surfactant. Colloid Surf A 2007;299:268–75. [17] Su JF, Dong H, Wang XY. Influence of temperature on the deformation behaviors of melamine-formaldehyde microcapsules containing phase change material. Mater Lett 2012;84:158–61. [18] Su JF, Huang Z, Ren L. High compact melamine-formaldehyde microPCMs containing n-octadecane fabricated by a two-step coacervation method. Colloid Polym Sci 2007;285:1581–91. [19] Herrington PR. Diffusion and reaction of oxygen in bitumen films. Fuel 2012;94:86–92. [20] Karlsson R, Isacsson U. Laboratory studies of diffusion in bitumen using markers. J Mater Sci 2003;38:2835–44.
Contents lists available at ScienceDirect
Construction and Building Materials journal homepage: www.elsevier.com/locate/conbuildmat
Investigation the self-healing mechanism of aged bitumen using microcapsules containing rejuvenator Jun-Feng Su a,⇑, Erik Schlangen b, Ying-Yuan Wang a a b
Department of Polymer Materials, School of Material Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, China Department of Materials and Environment, Faculty of Civil Engineering & Geosciences, Delft University of Technology, 2628CN Delft, The Netherlands
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
The microcapsules containing
The capillarity behaviors of rejuvenator in self-healing bitumen by microcapsules, (a–c) a microcrack was generated by liquid N2 with the width about 10–15 lm, the microcrack propagates and pierce the shells of microcapsules, (d and e) the liquid of rejuvenator leaked out from microcapsules and flowed into the microcapsules, and (f) movement trace and direction of rejuvenator during the capillarity.
rejuvenator can be broken by microcracks. With the help of capillarity, the rejuvenator can fill the microcracks. With the help of the penetration of rejuvenator, the aged bitumen has a trance to recovery its virgin properties.
a r t i c l e
i n f o
Article history: Received 4 June 2014 Received in revised form 10 January 2015 Accepted 21 March 2015 Available online 31 March 2015 Keywords: Bitumen Self-healing Rejuvenator Microcapsules
a b s t r a c t The aim of this paper is to investigate the self-healing mechanism of aged bitumen using microcapsules containing rejuvenator. Various microcapsule samples were successfully fabricated and the mean size and shell thickness were adjusted. It was found that the shell thickness was not greatly affected by the core/shell ratios and the emulsion stirring rates. These microcapsules can survive in melting bitumen with a good thermal stability. Based on these data, a typical microcapsule sample, fabricated by 3000 r min1 with core/shell ratio of 2/1, was selected to investigate the self-healing mechanism. The whole self-healing process was observed including the crack generation, capillarity and the diffusion behaviors. The results showed that microcapsules broke by microcracks and leaked the oily–liquid rejuvenator into microcracks. With the help of capillarity, the rejuvenator filled the cracks with a movement speed mainly determined by the volume of microcapsules in bitumen. A diffusion phenomenon was also observed by using a fluorescence microscope. Properties of virgin and rejuvenated bitumen measurements confirmed that the aged bitumen can be partly recovered by the microcapsules containing rejuvenator. Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction ⇑ Corresponding author. Tel./fax: +86 22 26210595. E-mail addresses: [email protected], [email protected] (J.-F. Su). http://dx.doi.org/10.1016/j.conbuildmat.2015.03.088 0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
Every year about 95% of the almost 100 million tonnes of bitumen is applied in the paving industry where they essentially act
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as a binder for mineral aggregates to form asphalt [1]. One important issue need to be considered is the ageing of bitumen from climate and traffic in service life [2]. After years of usage, the stiffness of asphalt concrete increases while its relaxation capacity decreases, the binder becomes more brittle causing development of microcracks and ultimately cracking of the interface between aggregates and binder occurs [3]. The ageing problem of bitumen leads to pavement failure including surface raveling and reflective cracking. It will increase the expense of maintaining bituminous pavements [4]. Although part of aged asphalt can be recycled as an economic and environmentally sound solution, it is still a big problem to deal with the hazardous material of aged asphalt in large quantities. Therefore, preservation and renovation bitumen of pavement is a low-cost and effective approach. An increase in the application of a higher percentage of the preservation and renovation of asphalt pavement is achievable using a rejuvenator. It is the only one method that can restore the original properties of the pavements [5]. The most important goal of utilizing rejuvenator products is to restore the asphaltenes/maltenes ratio. Rejuvenating agents have the capability of reconstituting the binder’s chemical composition and consist of lubricating and extender oils containing a high proportion of maltene constituents [6]. However, a rejuvenator is not successfully applied because it is hard to penetrate the pavement surface. Shen et al. [7] reported the results of using three rejuvenators. It was found that none could penetrate into the asphalt concrete more than 2 cm. When applying these materials, the road must be closed for some time after their application. The rejuvenator, at the same time, will cause a high reduction of surface friction of pavement for vehicles. Moreover, an important aspect of these rejuvenators is that they may be dangerous to the environment. Encapsulation rejuvenator inside-usage in asphalt may be an alternative approach. García et al. [8] reported a method to prepare capsules containing rejuvenator by using epoxy resin as coating and pours sand as skeleton. We reported a method to fabricate microcapsules containing rejuvenator utilizing methanol modified melamine–formaldehyde (MMF) resin as shell material [9]. These microcapsules had satisfactory thermal stability in bitumen and reliable mechanical properties resisting the mixing process and temperature changes [10]. It had been proved that this product was environmental-friendly powder encapsulating suitable size rejuvenator for chemical engineering and construction engineering [11]. Self-healing materials based on microcapsules have been studied widely which have structurally incorporated ability to repair damage caused by mechanical usage over time. Monomer is encapsulated and embedded within the matrix materials. When the crack gets to the microcapsule, the capsule breaks and the monomer bleeds into the crack, where it can polymerize and mend the crack [12]. Besides the similar structure of microcapsules self-healing materials for bitumen/microcapsules materials, we still need to consider their special self-healing mechanism. Microcapsules in bitumen can be broken by microcracks, then the released rejuvenator seals the microcracks and permeate surrounding bitumen. The capillaries and penetration behavior will determine the self-healing efficiency of aged bitumen [13]. With the help of capillarity, rejuvenator flows into narrow microcracks without the assistance of, and in opposition to, external forces. Firstly, the core–shell structure of microcapsules is taken into account for the specific requirement such as size distribution, encapsulation ratios and non-biodegradable property, since this influences their service performance. As bitumen acts as thin layers between aggregates which are usually less than 50 lm, size of microcapsules containing rejuvenators should be smaller than 50 lm to avoid being squeezed or pulverized during asphalt forming. Secondly, the shell thickness must be controlled to make sure that the microcapsules have excellent thermal stability. It was reported have found that
thicker shell will enhance the mechanical properties of microcapsules, the microcracks may not able to break these microcapsules [14]. It must be prevented that the microcracks propagation will go round the shells. In view of the above, the aim of this paper is to investigate the self-healing mechanism of aged bitumen using microcapsules containing rejuvenator. Various microcapsule samples were fabricated to optimize the core–shell structures. In order to observe the selfhealing behaviors, liquid nitrogen was used to generate microcracks in aged bitumen. The effects of mean size and shell thickness of microcapsules were evaluated to understand the self-healing behaviors. At the same time, the capillaring and penetration behaviors were analyzed to evaluate the rejuvenator movement. Properties of virgin and rejuvenated bitumen were compared to evaluate of recovery for aged bitumen. 2. Experimental 2.1. Materials The shell material was commercial prepolymer of melamine–formaldehyde modified by methanol (solid content was 78.0%) purchased from Aonisite Chemical Trade Co., Ltd. (Tianjin, China). The core material used as rejuvenator is dense, aromatic oil (density is 0.922 g/cm3, viscosity is 4.33 Pa s) obtained from Petro plus Refining Antwerp (800DLA, Belgium). Styrene maleic anhydride (SMA) copolymer (ScripsetÒ 520, Hercules, USA) was applied as dispersant. A small percentage of the anhydride groups have been established with a low molecular weight alcohol and it is fine, off-white, free flowing powder with a faint, aromatic odor [15]. The bitumen used in this study was 80/100 penetration grade obtained from Kuwait Petroleum. The aged bitumen 40/50 penetration grade was artificially produced by thin film oven test. The 40/50 aged bitumen was then blended with microcapsules using a propeller mixer for 30 min at 160 °C with a constant speed of 200 r min1. 2.2. Microencapsulation procedure The method of fabrication microcapsules containing rejuvenator by coacervation proceed can be divided into three steps [16]: (1) SMA (10.0 g) was added to 100 ml water at 50 °C and allowed mix for 2 h. Then a solution of NaOH (10%) was added dropwise adjusting its pH value to 10. The above surfactant solution and rejuvenator were emulsified mechanically under a vigorous stirring rate for 10 min using a high-speed disperse machine. (2) The encapsulation was carried out in a 500 ml three-neck round-bottomed flask equipped with a condensator and a tetrafluoroethylene mechanical stirrer. The above emulsion was transferred in the bottle, which was dipped in a steady temperature flume (room temperature). Half of MMF prepolymer (16 g) was added dropwise with a stirring speed of 500 r min1. After 1 h, the temperature was increased to 60 °C with a rate of 2 °C min1. Then another half of prepolymer (16 g) was dropped in a bottle at the same dropping rate. (3) The temperature was increased to 75 °C. After polymerization for 1 h, the temperature was decreased slowly at a rate of 2 °C min1 to ambient temperature. At last, the resultant microcapsules were filtered and washed with pure water and dried in a vacuum oven. 2.3. Morphologies observation An optical microscope (BX41-12P02, OLYMPUS) was used to check the fabrication process of microcapsules in emulsion. About 1 ml of the colloidal solution was extracted and spread on a clean glass slide (1 3 cm). The dried microcapsules were adhered on a double-side adhesive tape without cracking the shells. The surface morphologies were observed by using an Environmental Scan Electron Microscopy (ESEM, Philips XL30) at an accelerated voltage of 20 kV. 2.4. Mean size and shell thickness of microcapsules The mean size of microcapsules was measured by a laser particle size analyzer (HELOS-GRADIS, SYMPATEC GMBH, Germany). About 2 g microcapsules was mixed in 5 g epoxy resin. After the composite was dried at room temperature, it was carefully cut to obtain the cross-section. The thickness of shells can be measured from the ESEM images of cross-section of microcapsules [17]. At least 20 shells of each microcapsule sample were measured and the average data were calculated. 2.5. Thermogravimetric analysis (TGA) The thermal stability characterization of microcapsules was performed on a Dupont SDT-2960 Thermogravimetric analysis (TGA) at a scanning rate of 5 °C min1 in a flow of 40 ml min1 nitrogen (N2).
J.-F. Su et al. / Construction and Building Materials 85 (2015) 49–56 2.6. Microcracks generation in aged bitumen A thin bitumen/microcapsules sample was adhered on a glass sheet. It was carefully poured with a drop of liquid nitrogen (N2) at one end. Microcracks were quickly generated in this sample because of the low temperature brittleness. 2.7. Observation of rejuvenator movement in bitumen Capillarity and diffusion behaviors of rejuvenator in aged bitumen were observed by a fluorescence microscope (CKX41-F32FL, OLYMPUS) using the light characters such as reflection, diffraction and refraction. The scale of fluorescence microscope was applied to measure the size of capillarity and diffusion. As bitumen is a temperature-sensitive material, the observation is in an environment of 0 °C temperature. 2.8. Characterization of virgin and rejuvenated bitumen The properties of virgin bitumen, aged bitumen and rejuvenated bitumen were tested including penetration (ASTM D5), softening point (ASTM D36) and viscosity (ASTM D4402). To simply the research, it was assumed that the rejuvenator in microcapsules had totally been consumed during rejuvenation. The encapsulated rejuvenator in this study is yellow oil without solubility in water. At the end of the fabrication, the un-encapsulated rejuvenator is floating on the surface of emulsion. It was absorbed out using a syringe. Encapsulation efficiency (E) of rejuvenator was calculated by Eq. (1),
E¼
W1 W2 100% W1
ð1Þ
where W1 is the original weight of rejuvenator and W2 is the residue weight of rejuvenator.
3. Results and discussion
51
rejuvenator dispersed by ESEM under a 3000 r min1 emulsion rate. It was observed that the organic core material is dispersed into particles in water. After being encapsulated by shell material as showed in Fig. 1(b), the microcapsules are ultimately separated through the regulation of hydrolyzed SMA molecules with core/ shell ratio of 2/1. Fig. 1(c) shows the final dried microcapsules with regular globe shape with smooth surfaces. The mean size is an important parameter for microcapsules containing rejuvenator influencing their application possibility in asphalt. Too tiny size will limit the encapsulated content of rejuvenator. In another case, large microcapsules may be broken in mixing with asphalt concrete. Fig. 2 shows the ESEM morphologies of microcapsules (core/shell ratio of 3/1) with different mean sizes fabricated under emulsion stirring rates of 1000, 2000 and 3000 r min1. It can be seen that the mean sizes decreased sharply with the decreasing of stirring rates because higher stirring rates will smash the oily rejuvenator into smaller droplets. The rejuvenator applied in this study as core material still obeys this rule. Fig. 3 shows shell thickness data of microcapsules. The results suggest that the shell thickness is not greatly influenced by the stirring rates. As the formation of a shell is a coacervation process, the shell thickness is dominated by the amount of shell material. Less core/ shell ratio leads to a higher shell thickness value. It can be concluded that the core/shell ratios nearly do not affect the average size of microcapsules. In other words, the mean size is primarily decided by the core material disperse speed. Therefore, a typical microcapsule sample (fabricated with 3000 r min1 and core/sell ratio of 2/1) was applied to investigate the self-healing mechanism of aged bitumen.
3.1. Characterization of microcapsules containing rejuvenator 3.2. Thermal analysis of microcapsules SMA was applied as a nonionic dispersant by in situ polymerization method in this study. SMA molecules can hydrolyze in water by NaOH and form carboxyl (–COOH) groups. These hydrophilic polar groups, alternatively arranging along the SMA backbone chains, thus associate with water molecules and trimly cover the oil droplets surface with hydrophobic groups oriented into oil droplets and hydrophilic groups out of oil droplets [18]. Optical microphotographs of microcapsules were taken to illuminate the encapsulation details. Fig. 1(a) shows the morphology of
TGA has been extensively applied to investigate the encapsulation effect and shell compactness of microcapsules [10]. The microcapsule sample was composted with increasing temperature according to present residual weight (wt.%). It has been reported in our previous work that this rejuvenator has a marked weight loss between 337 °C and 469 °C owing to the evaporation of oil substance under elevated temperature. Fig. 4(a) shows the typical TGA curve of microcapsule sample fabricated with emulsion rate
Fig. 1. Optical morphologies of microcapsules containing rejuvenator fabrication process, (a) rejuvenator dispersed by ESEM under a 3000 r min1 emulsion stirring rate, (b) microcapsules with core/shell ratio of 2/1, and (c) dried microcapsules with regular globe shape with smooth surfaces.
Fig. 2. ESEM morphologies of microcapsules containing rejuvenator fabricated under emulsion rates of: (a) 1000 r min1 (b) 2000 r min1 and (c) 3000 r min1.
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3.3. Capillarity behaviors of rejuvenator in microcracks
Fig. 3. Shell thicknesses of microcapsules fabricated under various stirring rates.
In order to figure out more details of microcracks generation and the capillarity behaviors of rejuvenator, a bitumen/microcapsules composite (5/95, w/w) was observed continuously by a fluorescence microscope under temperature of 0 °C. The microcapsules were fabricated under core material stirring rate of 3000 r min1 with core/shell ratio of 2/1. As show in Fig. 6(a–c), a microcrack was generated by liquid N2 with a width about 10–15 lm. It propagated successfully and pierced the shells of microcapsules. We can distinguish between rejuvenator and bitumen from the morphology colors of fluorescence microscope, rejuvenator is green and bitumen is yellow. As can be seen in Fig. 6(d and e), liquid rejuvenator leaks out from microcapsules and flows into the microcrack. During a period of time, rejuvenator fills the microcrack and then spread the whole microcrack through capillarity. Especially in Fig. 6(f), we can clearly recognize the movement traces and direction of rejuvenator during the capillarity. To confirm the existence of the capillarity, we compared the states of microcrack in 60 min under 0 °C. Fig. 7(a) shows the original state of a microcrack in bitumen/microcapsules sample with a width of 20 lm. The crack was an arc curve in the sample. Interestingly, the crack is green color after 60 min (Fig. 7b) because it has been filled with rejuvenator coming out from broken microcapsules. Besides the confirmation of the capillarity, we also want to evaluate the extent and rate of rejuvenator through capillarity in microcracks. It is well known that the height L of a liquid column of capillarity is given by Eq. (2),
L¼
Fig. 4. Thermal stability of microcapsules, (a) the TGA plot of pure rejuvenator, (b– d) ESEM morphologies of microcapsules under various temperatures.
of 3000 r min1 and core/shell ratio of 2/1. The TGA curve may reflect thermal stability and structure of polymeric shell. Fig. 4(b and c) show ESEM morphologies of microcapsules under temperatures of 100 °C, 300 °C and 400 °C. It can be seen that the microcapsules still keep the global shape under 300 °C without break. Nearly about 10% weight is lost less than 100 °C for all microcapsule samples because of the evaporation of water and small molecules. The decomposite temperature is at about 396 °C (Fig. 4(d)). This degradation temperature is higher than the melting temperature of bitumen at 180 °C. It indicates the cured MMF resin will not be thermal decomposed mixing with melting asphalt. With the temperature increasing, the shell will firstly crack or broken under high temperature before decomposition. To verify the thermal stability of microcapsules in bitumen, the microcapsules were mixed with melting bitumen under various temperatures for 30 min. Then the shape of microcapsules was observed by an optical microscope. The microcapsules had an average size about 16 lm fabricated under core material stirring rate of 3000 r min1 (core/shell ratio of 2/1). In Fig. 5(a), it can be seen that microcapsules survived in bitumen under temperature 140 °C. With the increasing of temperature to 160 °C (Fig. 5b), 180 °C (Fig. 5c) and 200 °C (Fig. 5d), the microcapsules still kept their global shape without crack and thermal decomposition. These results indicate that microcapsules can resist the thermal effect of bitumen in application.
2c cos h qgr
ð2Þ
where c is the liquid–air surface tension, h is the contact angle, q is the density of liquid, g is local gravitational field strength, and r is radius of tube (crack). However, this rule cannot guide capillarity in self-healing bitumen. Because the microcapsules were homogeneously distributed in bitumen, the rejuvenator could quickly disperse from both sides of a crack. Therefore, we pay more attestation to the time (t) that rejuvenator can finally fill the whole microcrack. When a dry porous material such as a brick or a paper, is brought into contact with a liquid, it will start absorbing the liquid at a rate which decreases over time. For a bar of material with cross-sectional area A that is wetted on one end, the cumulative volume V of absorbed liquid after a time t is,
pffiffi V ¼ AS t
ð3Þ
where S is the sorptivity of the material. As rejuvenator is oily liquid, it may take a longer time for it to disperse due to its high viscosity. Another issue needs to be considered is the volume of microcapsules in bitumen. With higher volume ratio of microcapsules (Vm), the microcrack will, at the same time, have a higher probability to meet microcapsules. Summary of the above-mentioned laws, it can be drawn a conclusion that the capillarity time (T) for microcapsules self-healing material is determined by three aspects including the properties of liquid (M, related to viscosity and contact angle), the volume of cracks (V0 , related to width and length) and the volume ratios of microcapsules in medium. T can be written as an equation,
T ¼ f ðM; V 0 ; V m Þ
ð4Þ
To simplify this complex problem, bitumen/microcapsules samples were prepared with various Vm values to measure the capillarity speeds of rejuvenator. The movement time of rejuvenator is measured to determine the speed of the capillarity using the scale of fluorescence microscope. We investigated both the speeds of the lateral-movement (Fig. 8a) and longitudinal-movement (Fig. 8b) in microcracks under
J.-F. Su et al. / Construction and Building Materials 85 (2015) 49–56
53
Fig. 5. Optical morphologies of microcapsules in melting bitumen under different temperatures for 30 min.
Fig. 6. The capillarity behaviors of rejuvenator in self-healing bitumen by microcapsules, (a–c) a microcrack was generated by liquid N2 with the width about 10–15 lm, the microcrack propagates and pierce the shells of microcapsules, (d and e) the liquid of rejuvenator leaked out from microcapsules and flowed into the microcapsules, and (f) movement trace and direction of rejuvenator during the capillarity.
temperature of 0 °C. The width and length data in Fig. 8 were measured by a fluorescence microscope with scale. In Fig. 8(a and b), the arrows point the directions and tracks of rejuvenator movement. Fig. 8c shows the relationship between the lateral-movement time and the volume of microcapsules (5, 10, 15, 25 and 30 vol.%) in microcracks (width 10, 20 and 30 lm), respectively. The time data were carefully recorded by observing the rejuvenator movements under a fluorescence microscope with a scale. Firstly, it can be known that rejuvenator need more time to complete a lateralmovement in wider microcracks. For example, the times are 67, 54, and 46 min for samples with 5 vol.% microcapsules in microcracks with width of 30, 20 and 10 lm. Secondly, higher volume ratio of microcapsules leads the rejuvenator to take less time for a lateralmovement. The reason may be that more rejuvenator has released out into microcracks and the releasing area is improved. Fig. 8(d)
shows the relationship between the longitudinal-movement time and the volume of microcapsules (5, 10, 15, 25 and 30 vol.%) in microcracks (length 100, 200, 300 lm), respectively. Higher volume ratio of microcapsules also leads the rejuvenator need less time to complete a longitudinal-movement. At the same time, it has been seen that a longer microcrack make the rejuvenator need more time to complete a long-distance movement. However, higher volume ratio of microcapsules (>25 vol.%) will weaken this trend. We can attribute this phenomenon to the mass increasing of rejuvenator in a microcrack. 3.4. Observation of rejuvenator diffusion in aged bitumen Mass transfer by molecular diffusion is one of the basic mechanisms in many branches of science. Molecular diffusion is a
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Fig. 7. Fluorescence microscope morphologies capillarity behavior of rejuvenator in a microcrack, the states of a microcrack in bitumen/microcapsules sample with a width of 20 lm before (a) and after (b) 60 min, the microcrack has been filled with rejuvenator out of microcapsules.
Fig. 8. The capillarity speeds of rejuvenator in bitumen microcracks under temperature of 0 °C, (a and b) the illustrations of the lateral-movement and longitudinalmovement, (c) the relationship between the lateral-movement time and the volume of microcapsules (5, 10, 15, 25 and 30 vol.%) in microcracks (width 10, 20 and 30 lm), and (d) the relationship between the longitudinal-movement time and the volume of microcapsules (5, 10, 15, 25 and 30 vol.%) in microcracks (length 100, 200, 300 lm).
transport property which monitors the rate of mass transfer of species in a medium [19]. In addition, it was reported that the diffusion behaviors of bitumen has great relationship with temperature, viscosity of the diffusion medium, diffusant size and polarity [20]. In this study, we only observe the diffusion processes in order to design and plan microcapsules based bitumen recovery processes, because it is required for determining the rate of mass transfer between the rejuvenator and aged bitumen at given conditions. The diffusion coefficient between liquid–solid phases is mainly determined by liquid molecular structure, solid structure, temperature and pressure. Fig. 9 shows the fluorescence microscope morphologies of rejuvenator leaked out from microcapsules diffusion in aged bitumen at 0 °C for 24 h. A microcrack was generated in this aged bitumen sample previously. It can be
confirmed in Fig. 9(a) that the microcapsules were broken by the microcrack and the rejuvenator flowed out. The diffusion areas were also observed after a period of 24 h. Interestingly, we even can identify the diffusion direction of rejuvenator coming outing of a microcapsule into the aged bitumen as seen in Fig. 9(b). A gradient diffusion layer exists between the rejuvenator and the matrix. Normally, diffusion behavior of binary materials is reflected in its phase diagram. The composition of the phases is dependent on the phase-structures and the temperature, the phase-structures being the border between the one- and twophase regions. Therefore, it can be concluded that various conditions including the aging degree of bitumen and the diffusion temperature. The diffusion coefficient will be discussed in our subsequent research.
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Fig. 9. Fluorescence microscope morphologies of rejuvenator diffusion in aged bitumen at room temperature for 24 h.
Table 1 Properties of virgin and rejuvenated bitumen (penetration value, softing point value, viscosity value).
Penetration (d-mm, 25 °C) Softening point (°C) Viscosity (135 °C) (mPa s)
Original Bitumen (80/100)
Aged bitumen (40/50)
86 46.7 325
43 53.5 578
3.5. Properties of virgin and rejuvenated bitumen In addition to an analysis of rejuvenator diffusion, we wished to evaluate the results of rejuvenating aged bitumen. Efficiency of the rejuvenator depends on its viscosity and the quantity added to the aged bitumen and thus we decided to conduct a preliminary investigation to explore the effects of blending known quantities of rejuvenator with penetration grade bitumen on binder rheology. To this purpose, a series of microcapsules/bitumen samples were first heated at 200 °C for 12 h and then stored for 60 days. The microcapsules applied in this test had an encapsulation ratio of 85% with an average size of approximately 20 lm and had been fabricated under conditions of stirring rate of 3000 r min1 and core/ shell ratio of 1/2. Based on the previous investigation results, it was predicted that the majority of the encapsulated rejuvenator would leak out of the spheres and penetrate into the aged bitumen. The subsequent rejuvenating effect was assessed by comparing the properties of aged bitumen samples under the same conditions. In this study, the original bitumen (80/100) was found to have penetration, softening point and viscosity values of 86 d-mm, 46.7 °C and 325 mPa s. In contrast, the aged bitumen (40/50) had values of 43 d-mm, 53.5 °C and 578 mPa s. The aged bitumen was subsequently rejuvenated with microcapsules at 2–10% by weight of bitumen. Table 1 lists the penetration, softening point and viscosity of the aged bitumen before and after rejuvenation with varying amounts of microcapsules. These data demonstrate that the penetration value increased as the amount of microcapsules In the aged bitumen increased. This result is attributed to a reduction in the ratio of asphaltenes to maltenes. The addition of approximately 10% microcapsules returns the aged 40/50 bitumen to a condition similar to that of the original bitumen. Additionally,
Rejuvenated aged bitumen with microcapsules (wt.%) 2
4
6
8
10
12
50 51.0 573
63 50.3 552
64 49.2 500
70 47.1 470
76 46.6 406
80 45.4 390
the softening point value decreased with the addition of microcapsules. In the aged bitumen, increases in the level of high molecular weight asphaltenes tend to produce a harder material with lower temperature susceptibility and thus increase the softening point. The addition of the rejuvenator, however, is evidently capable of mitigating this effect. Lastly, although the aged bitumen had a high viscosity value, the addition of 10% microcapsules returned the viscosity to 390 mPa s. Therefore the same workability is expected from the rejuvenated bitumen.
4. Conclusions The self-healing mechanism of aged bitumen using microcapsules containing rejuvenator was investigated. The effects of mean size and shell thickness of microcapsules were evaluated for selfhealing behaviors and capillaries and penetration behaviors were analyzed to evaluate the rejuvenator movements. From the mentioned preliminary results, the following conclusions can be drawn, (1) The shell thickness of microcapsules was not greatly affected by the core/shell ratios and the emulsion stirring rates. These microcapsules can survive in melting bitumen with a good thermal stability. This result means that the microcapsules can practically be applied in bitumen without broke before usage. (2) The microcapsules can be broken by microcracks and leaked the oily-liquid rejuvenator into microcracks. With the help of capillarity, the rejuvenator filled the cracks with a movement speed mainly determined by the volume of microcapsules in bitumen.
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(3) Higher volume ratio of microcapsules leads the rejuvenator need less time to complete a longitudinal-movement. (4) With the help of the penetration of rejuvenator, the aged bitumen has a trance to recovery its virgin properties.
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