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Progress in experimental investigations on evaporation characteristics of a

fuel droplet

Article  in  Fuel Processing Technology · March 2022

DOI: 10.1016/j.fuproc.2022.107243

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 1 Progress in experimental investigations on evaporation
2 characteristics of a fuel droplet
3

4 Zhaowen Wang1,2*, Bo Yuan1,2, Yuhan Huang3, Junhui Cao1,2, Yuzhou Wang1,2,

5 Xiaobei Cheng1,2*

1
8 State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology,
9 Wuhan, 430074, China
2
10 School of Energy and Power Engineering, Huazhong University of Science and Technology,
11 Wuhan, 430074, China
3
12 Centre for Green Technology, School of Civil and Environmental Engineering, University of
13 Technology Sydney, NSW 2007, Australia

14

15

16 * Corresponding author:

17 Dr. Zhaowen Wang, Email: [email protected] , Phone: +86 15827580480

18

19 Please cite this article as:

20 Zhaowen Wang, Bo Yuan, Yuhan Huang, Junhui Cao, Yuzhou Wang, Xiaobei Cheng.
21 Progress in experimental investigations on evaporation characteristics of a fuel droplet. Fuel
22 Processing Technology 2022; 231: 107243.DOI:https://doi.org/10.1016/j.fuproc.2022.107243

1
23 Abstract

24 Investigating the evaporation characteristics of a fuel droplet is critical for understanding

25 spray and combustion processes, which provides valuable information and guidance for
26 optimizing engine performance. This paper systematically reviews the droplet evaporation
27 characteristics of various fuels. Firstly, experimental methods for fuel droplet evaporation are
28 introduced, including flying droplet, suspension and levitation, of which the latter two are the
29 most widely applied due to their simple setups and convenient measurements. Secondly, droplet
30 evaporation mechanisms of different fuels are comprehensively discussed. The evaporation
31 process of single-component fuel droplets includes transient heating and equilibrium
32 evaporation phases. Miscible and immiscible multi-component fuel droplets could experience
33 puffing and micro-explosion phenomena, which increase droplet surface area and evaporation
34 rate. Droplet evaporation may be the best when light component concentration is around 50%
35 due to the strongest puffing and micro-explosion. The water droplets in emulsified fuel are
36 slightly superheated by 0 to 30 ºC when micro-explosion occurs. Nanoparticles could enhance
37 droplet evaporation at low concentrations (0-1.25%) but inhibit droplet evaporation at higher
38 concentrations. Finally, future research directions of fuel droplets are elaborated. More
39 advanced experimental and numerical methods should be developed. Meanwhile, investigations
40 on droplet evaporation should be combined with spray and combustion.

41

42 Keywords: Liquid fuels; Fuel droplet; Evaporation characteristics; Puffing; Micro-

43 explosion

44

2
45 Highlights

46 • Evaporation of single-component droplet includes transient heating and equilibrium

47 evaporation.

48 • Puffing and micro-explosion promote evaporation of multi-component fuel droplet.

49 • Bubble growth and rupture cause micro-explosion of miscible multi-component fuel

50 droplet.

51 • The dispersed phases in emulsion droplet aggregate and coalesce before micro-explosion.

52 • A lower concentration of nanoparticles enhances the evaporation rate of nanofluid fuel

53 droplet.

54 Graphical abstract

55
56

3
57 Nomenclature

CO Carbon monoxide
PM Particulate matters
NOx Nitrogen oxides
HC Hydrocarbons
ICE Internal combustion engine
OA Oleic acid
LA Linoleic acid
ABE Acetone-butanol-ethanol
FAME Fatty acid methyl ester
BD Biodiesel
GTL Gas-to-liquid
d Instantaneous droplet diameter
Support diameter

Thermocouple diameter

Initial droplet diameter

κ Thermal conductivity

K Evaporation rate constant

t Heating time
m Mass
ρ Density
V Volume
/ Normalized square diameter
t/ Normalized time
58

4
59 1. Introduction

60 The rapid population and economic growth promote the use of automobiles for
61 transportation, which greatly increases the proportion of energy consumed by automobiles in
62 the total energy consumption from 23% in 1971 to 29% in 2015 [1, 2], emitting a large amount
63 of greenhouse gas emissions that cause global warming [3]. Meanwhile, the rapid increase in
64 the number of automobiles also poses a significant burden on the environment. Harmful exhaust
65 emissions such as carbon monoxide (CO), particulate matters (PM), nitrogen oxides (NOx) and
66 hydrocarbons (HC) have caused serious air pollution [4, 5]. These problems are threatening
67 human health and survival [6, 7]. Therefore, improving the thermal efficiency and emissions
68 performance of internal combustion engines (ICEs) has become one of the hottest issues
69 concerned by the engine industry worldwide [8]. In recent years, searching for alternative fuels
70 such as biodiesels [9-11], alcohol fuels [12, 13] and emulsified fuels [14] is a major promising
71 solution for energy saving and emissions reduction of ICEs.

72 As far as liquid fuels are concerned, the form of their utilization in ICEs is to convert
73 chemical energy into heat energy through combustion, which drives the piston to output useful
74 work. Consequently, the quality of combustion process determines the performance of ICEs,
75 including torque, fuel economy and pollutant emissions. Fuel cannot be fully utilized under a
76 poor combustion, leading to decreases in output power and increases in fuel consumption and
77 pollutant emissions. Improving the spray evaporation characteristics of liquid fuels is the key
78 to optimize engine combustion [15].

79 Spray evaporation refers to the process that a fuel is injected by an injector to generate a

80 jet, which breaks up due to aerodynamic forces, and finally disperses into a large number of

81 droplets and mixes with air to form a combustible mixture [16]. However, it is difficult to

82 quantitatively investigate the spray evaporation characteristics by experimental methods due to

83 its complexity. Therefore, investigations on the evaporation of a fuel droplet are often used as

84 an alternative for revealing the underlying mechanisms of those processes [17]. In fact, many

85 droplets are formed after spray atomization and breakup, and droplet evaporation is the basis

86 and determines the performance of spray evaporation [18]. Therefore, investigations of a fuel

87 droplet are critical for characterizing and understanding spray evaporation [19]. Moreover,

88 spray eventually develops into discrete droplets that are far apart [20], which makes the

5
 89 hypothesis of an isolated droplet reasonable. It is often necessary to study a droplet first when

90 studying the influence of engine operating conditions on fuel evaporation process [21].

91 Consequently, investigations on the heating and evaporation processes of fuel droplets are of

92 great significance for improving engine performance [22].

93 Many scholars have studied the fuel evaporation characteristics by investigating a fuel
94 droplet. A few reviews have also been published on specific aspects of droplet evaporation,
95 which can be divided in experimental studies and mathematical modelling.

96 1.1. Experimental investigations

97 Experimental investigations on the evaporation process of a fuel droplet provide the first
98 hand information on its evaporation characteristics, which is of significance for the applications
99 of a fuel in real engines. They also provide valuable information for the development and
100 validation of droplet/spray evaporation and combustion models. Thus, experimental
101 investigations are widely adopted for understanding the fuel droplet evaporation processes.
102 Birouk and Gokalp [23] introduced the effect of turbulence intensity on evaporation of a fuel
103 droplet. Téré et al. [24] described evaporation phenomenon and mechanisms of an isolated fuel
104 droplet and the impacts of natural and forced convection. Basu and Miglani [25] reviewed the
105 thermo-physical processes during the evaporation of a nanofluid fuel droplet and their
106 influencing factors (e.g. nanoparticle concentrations and types). Emekwuru [26] reviewed the
107 evaporation mechanisms of a nanofluid fuel droplet. It was summarized that nanoparticles could
108 facilitate droplet evaporation by increasing heat transfer to the droplet by radiation absorption
109 and causing droplet micro-explosion. Wang et al. [27] discussed the impact of nanoparticles on
110 fuel droplet evaporation at different ambient temperatures. They reported that nanoparticles
111 inhibited droplet evaporation at low temperatures, but increased droplet evaporation at high
112 temperatures due to micro-explosion.

113 1.2. Mathematical modelling

114 Mathematical modelling of fuel droplets could quantify the amount of evaporated fuel and
115 visualize its mixing and distribution in the ambient air, leading to more accurate simulations
116 under actual engine conditions. Therefore, numerical simulations were also commonly used to
117 understand the heating and evaporation of fuel droplets. Sazhin et al. [28] presented liquid and
118 gas phase models for fuel droplet heating and evaporation. Raghavan [29] reviewed the
119 numerical models that were used to simulate evaporation process of a fuel droplet under high

6
120 pressure conditions. Sazhin [30] introduced the modelling methods for the droplet evaporation
121 process, including Discrete Component Model (DCM) and Multi-Dimensional Quasi-Discrete
122 Model (MDQDM), and their applications for different fuel droplets. The development of gas
123 phase evaporation model was discussed and some unsolved problems were also proposed. Al
124 Qubeissi et al. [31] described DCM, MDQDM, Complex Fuel Surrogate Model (CFSM),
125 Transient Multi-Dimensional Quasi-Discrete Model (TMDQDM) and their implementations
126 into numerical codes.

127 1.3. Motivation and outline of this review

128 The above reviews mostly focused on the evaporation investigations of specific fuel
129 droplets (i.e. nanofluid fuel) and numerical investigations of fuel droplet evaporation. So far,
130 there is a lack of critical evaluation and review on experimental investigations of evaporation
131 characteristics of single- and multi-component fuel droplets. Recently, increasing experimental
132 investigations have been conducted to explore the evaporation characteristics of fuel droplets.
133 Therefore, this paper aims to systematically review and analyze the research findings on
134 evaporation characteristics of fuel droplets, including both single and multi-component fuels.
135 The multi-component fuels are further classified into miscible, liquid-liquid immiscible and
136 liquid-solid immiscible fuels. This paper focuses on the state-of-the-art progress on
137 experimental investigations of a fuel droplet with different components. This review should
138 provide helpful guidance on the scientific research and practical applications of fossil and
139 renewable fuels.

140 The remaining of this paper is organized as follows. Firstly, the experimental methods for
141 studying evaporation of fuel droplets are introduced and compared in Section 2. Secondly, the
142 evaporation characteristics of single-component fuel droplets are presented in Section 3. Then,
143 recent studies on evaporation characteristics of multi-component fuel droplets are reviewed,
144 including miscible (Section 4), liquid-liquid immiscible (Section 5) and liquid-solid immiscible
145 (Section 6) multi-component fuels. Finally, the challenges and future research directions on
146 evaporation of fuel droplets are elaborated in Section 7.

147

148 2. Experimental methods

149 Currently, there are mainly three experimental methods for studying the evaporation of a
150 fuel droplet, namely suspension, flying droplet and levitation. Table 1 compares the

7
151 mechanisms, advantages and limitations of these research methods. As shown in Table 1, each
152 method has its own advantages and disadvantages that determine their applications according
153 to the experiment needs and purposes. The suspension method (Fig. 1) uses an intersection of
154 quartz wires/fibers [19, 32], ceramic wires/fibers [33, 34] or junction of thermocouples [35-38]
155 as the support to hang a droplet for heating and evaporation. This method is simple to generate
156 a droplet under a static state, which is convenient for measurement of droplet parameters such
157 as diameter and temperature. The disadvantage is that the droplet size is usually much larger
158 than that produced in a real engine spray. In addition, the suspension support affects droplet
159 evaporation. Table 2 concludes the studies on the influence of support on droplet evaporation.
160 Generally, the support promotes droplet evaporation by increasing heat transfer to the droplet.
161 However, this impact can be ignored when the support size is sufficiently small (less than 1/10
162 of the droplet size) and thermal conductivity of support is low (less than 80W/m-K). The
163 suspension method is widely applied to investigate the evaporation characteristics of fuel
164 droplets under different working conditions.

165

166 Fig. 1. Schematic diagrams of different forms of suspension methods: (a) vertical
167 thermocouple, (b) cross-wire/fiber.

168 In the flying droplet method (Fig. 2), the droplet undergoes a free falling motion in the

169 experimental chamber. Images of the falling droplet are captured by a wide-angle fixed camera

170 or by changing the camera position. This method can produce relatively small droplet and

171 allows the droplet to evaporate freely without influence from any foreign parts (e.g. the

172 suspension support in Fig. 1). Moreover, there is no sealing problem for experiments under high

173 ambient pressure. However, the disadvantages are that it has high requirements for equipment

8
174 and it is difficult to measure some droplet parameters (e.g. temperature). The interactions

175 between the droplet and the surrounding flow field have great influences on the evaporation

176 process if the droplet is too small. When the droplet fell, there was a relative velocity between

177 droplet and surrounding gas. This meant that the droplet evaporated in a convective

178 environment, which promoted droplet evaporation and caused experimental error. Overall, the

179 flying droplet method has great advantages in simulating the evaporation process of an

180 atomized droplet in engine cylinders when compared with other methods.

181

182 Fig. 2. Schematic diagram of flying droplet method: (a) wide-angle fixed camera, (b) moving
183 camera.

184 The levitation method (Fig. 3) balances the buoyancy or magnetic force of a droplet with

185 its gravity by fuel vapor (i.e. Leidenfrost phenomenon), magnetic field or acoustic levitator, so

186 as to levitate the droplet. In this method, the droplet is approximately spherical and more stable

187 compared to the flying droplet method. Meanwhile, it has no foreign part disturbance compared

188 to the suspension method. It can also observe the droplet for a long time [39], which is suitable

189 for droplet evaporation investigation under atmospheric pressure. However, it takes time for the

190 levitation droplet to stabilize, during which the droplet will evaporate and the data is

191 unmeasurable. In particular, higher ambient temperature greatly increase the droplet mass loss

192 due to evaporation. Therefore, levitation method cannot be applied under high ambient

193 temperature conditions. Finally, if droplet was levitated by acoustic and magnetic fields, there

9
194 was a coupling effect of multiple fields, making it different from actual fuel droplet evaporation.

195

196 Fig. 3. Schematic diagram of the levitation method: (a) levitating by fuel vapor, (b) levitating
197 by acoustic levitator, (c) levitating by magnetic force.

198

199 Table 1. Comparison of research methods for fuel droplets.

Methods Mechanisms Advantages Disadvantages

Suspending droplets by Thermal conductivity of

Simple to generate droplets support
quartz wires,
Suspension Easy to measure droplet
thermocouples or other Large droplet size
fibers parameters
Ellipsoidal droplets
Simple to generate droplets
Free falling motion of No foreign part disturbance Difficult to measure droplet
Flying parameters
droplets in experimental Small droplet size
droplet
chamber Easy to achieve high pressure Droplet-air interactions
conditions
No foreign part disturbance
Levitating droplets by Coupling effect of multiple
Spherical droplet fields
Levitation buoyancy, magnetic or
acoustic force Easy to measure droplet Low ambient temperature
parameters

200

201 Table 2. Effect of suspension support on droplet evaporation.

Refs. Support materials Key results

Volkov and Copper, aluminum,
Support form and material affected heating and evaporation times,
Strizhak ceramics, steel and respectively.
[40] nichrome

Wang et al. Quartz, iron and Evaporation rate constant and lifetime were linearly correlated with
[41] copper and κ; Heat transfer of support would lead to micro-explosion when
>0.15 mm or κ>400 W/m-K; Support had little effect on evaporation

10
 when <0.10 mm and κ<80 W/m-K.
Chauveau et Support had little effect on droplet evaporation when using cross-fiber
Quartz fiber
al. [42] and =14 μm; Evaporation rate increased linearly with .
Droplets on thermocouples evaporated faster when was the same;
Rehman et Thermocouple and
Larger led to faster droplet evaporation; Influence of support could
al. [43] glass fiber
be ignored when / <0.01.
Han et al. Thermocouple and Droplets on thermocouples evaporated faster; Droplet evaporation rate
[44] quartz fiber increased first and then decreased with .
Symbols: , support diameter; , initial droplet diameter; κ, thermal conductivity; , thermocouple
diameter.

202

203 3. Evaporation characteristics of single-component fuel droplets

204 The evaporation of a droplet is usually characterized by the variation of droplet diameter
205 with time [45]. According to the classical droplet evaporation theory [46], it is necessary to
206 normalize droplet diameter and time to eliminate the influence of difference in initial droplet
207 diameter caused by surface tension and other factors [47]. In addition, droplet lifetime and
208 evaporation rate are also widely used to analyze the droplet evaporation process.

209 A single-component fuel refer to a fuel that only composes of one component, such as the
210 ethanol fuel and the n-hexadecane fuel. The evaporation processes of different single-
211 component fuels are similar, which demonstrate two stages. Ma et al [48] divided the
212 evaporation process of n-hexadecane droplet into transient heating and equilibrium evaporation
213 based on the variation of normalized square diameter (d2/d02) with normalized time (t/d02) at
214 523 K. They defined a critical point for heating process when d2/d02 was one. This was
215 consistent with the division of evaporation stages for oleic acid (OA) and linoleic acid (LA) by
216 Wang et al. [49]. Xi et al. [50] also divided the evaporation processes of n-hexadecane and n-
217 butanol droplets into transient heating and stable evaporation. However, Chaitanya and Basu
218 [51] defined the evaporation process of n-decane droplet as preheating and linear regression
219 regimes. Although the stage definitions may be different among scholars, there are common
220 features in each stage. In the first stage of droplet evaporation, the heat absorbed by droplet is
221 mainly used to increase its own temperature due to low droplet temperature [48] and only a
222 small part is used for evaporation. In this stage, the droplet temperature rises rapidly [50],
223 resulting in a decrease in the droplet density [52]. According to the relationship (i.e. V=m/ρ) of
224 mass (m), density (ρ) and volume (V), the droplet volume increases if the decrease in density
225 is greater than the mass loss caused by surface evaporation (i.e. thermal expansion rate is greater

11
226 than surface evaporation rate). Otherwise, the droplet volume decreases [53]. In the second
227 stage, the droplet temperature slowly approaches the boiling point and reaches a relatively
228 stable state since it cannot exceed the fuel boiling point [54], which is called a quasi-steady
229 state [53]. In this stage, all the absorbed heat is used for droplet evaporation. The d2/d02 of
230 droplet decreases linearly with t/d02 and the evaporation rate remains unchanged [48], following
231 the classical d2 law of = − K ∗ t where d is instantaneous droplet diameter, d0 is initial
232 droplet diameter, K is evaporation rate constant and t is heating time.

233 Many scholars have studied the impact of various factors on the evaporation of single-
234 component fuel droplet to comprehensively understand their evaporation mechanisms. This
235 section systematically reviews the effect of fuel properties, initial droplet diameter, ambient
236 temperature and pressure, and turbulence on the evaporation characteristics of single-
237 component fuel droplet.

238

239 3.1. Effect of fuel properties and initial droplet diameter

240 The differences in fuel properties lead to different evaporation behaviors. Generally, a
241 higher boiling point causes a longer first stage of droplet evaporation process, a more obvious
242 increase in diameter, a smaller evaporation rate and a longer lifetime. Ma et al. [48] found that
243 the diameter of n-hexadecane droplet (boiling point: 287 ℃) increased significantly during the
244 transient heating stage. Javed et al. [55] showed that the initial heating phase of n-heptane
245 droplet (boiling point: 98 ℃) was very short, and the expansion in droplet diameter was also
246 very small. Pinheiro et al. [21] reported that the transient heating phase of ethanol droplet
247 (boiling point: 78 ℃) was basically not observed. However, Wang et al. [49] discovered that
248 LA (boiling point: 407 ℃) had the shortest transient heating stage and OA (boiling point: 361 ℃)
249 had the longest transient heating stage at 873 K. The increase of LA droplet diameter was
250 smaller than that of OA droplet. Meanwhile, Ma et al. [48] observed that n-hexadecane droplet
251 (boiling point: 287 ℃) had shorter lifetime and higher evaporation rate than n-butanol droplet
252 (boiling point: 118 ℃) at 623 and 723 K, which was consistent with Xi et al. [50]. Patel and
253 Sahu [56] also found that although n-heptane had a higher boiling point than ethanol, its
254 evaporation rate was greater than that of ethanol at 609 K. This means that in addition to the
255 boiling point, other fuel properties, such as latent heat [48, 50, 57] and mass diffusivity [56],
256 also affect the droplet evaporation behaviors.

257 Initial droplet size affects evaporation surface area, thereby affecting the droplet lifetime
12
258 [45]. Verwey and Birouk [58] studied the impact of d0 on the evaporation rate of n-decane and
259 n-heptane droplets. The results indicated that the evaporation rate increased linearly with d0.
260 They suggested that droplet evaporation rate was affected by natural convection and molecular
261 diffusion. The former was linearly correlated with d3, while the latter did not theoretically
262 depend on d. The increase of initial droplet size may enhanced the contact area between
263 atmosphere and droplet, which promoted natural convection and thus increased the evaporation
264 rate [59].

265

266 3.2. Effect of ambient temperature and pressure

267 Ambient temperature determines the heat transfer between environment and droplet.
268 Droplets could absorb more heat under a higher ambient temperature, thus accelerating the
269 droplet evaporation and shortening the droplet lifetime. Chen et al. [60] found that n-decane
270 droplet evaporated faster at 703 K than that at 503K. Verwey and Birouk [58] reported that the
271 promoting effect of turbulence and initial droplet size on droplet evaporation was weakened
272 with the increase of temperature, indicating that temperature had a greater influence on droplet
273 evaporation compared with other factors. Ma et al. [48] concluded that the lifetimes of n-
274 hexadecane and n-butanol droplets decreased by 97% and 79%, respectively as ambient
275 temperature rose from 423 to 723 K, implying that ambient temperature had a greater effect on
276 fuel evaporation than boiling point.

277 Researchers have reached a consensus on the effect of ambient pressure on droplet lifetime,
278 i.e. droplet lifetime increases with ambient pressure. However, the results on evaporation rates
279 varied. Verwey and Birouk [58] reported that high pressure suppressed diffusion of fuel
280 molecular on the droplet surface. This contributed to a longer lifetime at ambient pressure of
281 10 bar than 1 bar. They found that the droplet evaporation rate gradually decreased as pressure
282 rose from 1 to 10 bar. The effect of higher ambient pressure (1-3 MPa) on n-hexadecane droplet
283 evaporation under the microgravity condition at 773 K was studied by Nomura et al. [53]. They
284 found that the evaporation rate decreased linearly with the ambient pressure when pressure was
285 greater than the fuel critical pressure of 1.41 MPa, which was due to the larger isobaric specific
286 heat capacity of fuel vapor near the critical point and the smaller difference in temperature
287 between droplet surface and experimental atmosphere. However, the evaporation rate increased
288 linearly with ambient pressure until it reached the critical pressure, which was due to the larger
289 heat conductivity of gas mixture and the smaller density and latent heat of fuel. Although the

13
290 evaporation rate improved with ambient pressure at subcritical condition, the droplet
291 evaporation lifetime prolonged. They explained that it was due to the fact that fuel boiling point
292 rose with ambient pressure, leading to the increase in the initial heating period that exceeded
293 the decrease in the quasi-steady evaporation stage.

294

295 3.3. Effect of turbulence

296 Turbulence can take away fuel vapor from droplet surface, which facilitates the formation
297 of vapor concentration gradient and thus promotes droplet evaporation. Marti et al. [61]
298 revealed that increasing turbulence intensity resulted in a slight improvement in the evaporation
299 rate of n-heptane. Patel and Sahu [56] found that the d2/d02 of ethanol, n-heptane and n-decane
300 droplets basically changed linearly with t/d02 under different turbulent kinetic energies,
301 suggesting that the d2 law was also applicable in turbulence. The evaporation rate also increased
302 with the turbulence intensity, while the degree of increase gradually decreased, because the
303 ability of vapor molecules to follow the fluid material reached their limit. They also observed
304 that turbulence had a greater effect on the evaporation of less volatile fuels, while fuel vapors
305 with larger mass diffusivity in the atmosphere were less influenced by turbulence. Rehman et
306 al. [43] confirmed that the effect of low convective velocity on droplet lifetime was greater than
307 that of high convective velocity, which was similar to the results reported in [56]. This may be
308 attributed to the reason that low convective velocity has a greater influence on the vapor
309 concentration gradient on droplet surface.

310

311 4. Evaporation characteristics of miscible multi-component fuel droplets

312 Miscible multi-component fuel is a mixture of two or more mutually soluble components.
313 Compared to single-component droplet, the diameter of multi-component droplet fluctuates
314 when it evaporates, which is caused by the different evaporation rates of each component due
315 to their different physical properties. When the droplet temperature is higher than the boiling
316 points of light components but lower than the boiling points of heavy components, the light
317 components evaporate inside the droplet to generate bubbles. The bubbles burst once the bubble
318 pressure is larger than the sum of droplet surface tension and ambient pressure, resulting in
319 different degrees of droplet breakup [45, 59, 62], such as puffing and micro-explosion. This
320 increases droplet surface area, thereby promoting droplet evaporation and shortening droplet

14
321 lifetime [63, 64]. This is of great significance in improving fuel atomization and combustion.

322 Zhang et al. [52] divided the evaporation process of biodiesel-butanol droplet into three
323 phases: transient heating, fluctuation evaporation and equilibrium evaporation, as shown in Fig.
324 4. In the first phase, the d2/d02 of droplet remained roughly constant due to the equilibrium
325 between the droplet evaporation and thermal expansion rates. In the second phase, the droplet
326 diameter fluctuated frequently. It was because not only the fuel on the droplet surface
327 evaporated, but also the light components inside the droplet evaporated to form bubbles which
328 grew up and burst, resulting in droplet expansion and breakup. This process continued until
329 butanol in the droplet was almost completely evaporated. The third phase was mainly the
330 evaporation of heavy components, causing the d2/d02 of droplet to decrease linearly which
331 followed the classic d2 law. Wang et al. [45] divided the evaporation process of soybean oil
332 droplet into four phases: transient heating, micro-explosion evaporation, equilibrium
333 evaporation and residue evaporation. Although the definitions of the first three phases were
334 different from Zhang et al. [52], the features of each phase were similar. The formation of
335 residue evaporation phase was mainly due to the decomposition of macromolecular substances
336 in the fuel into small free radicals at high temperature, followed by free radical polymerization
337 to produce viscous gelatinous substances [65].

338

339 Fig. 4. Variation of the normalized squared diameter of biodiesel-butanol droplet with the
340 normalized time at 1073 K [52].

341 In this section, the effect of various factors on the evaporation characteristics of miscible
342 multi-component fuel droplets is reviewed and the relevant studies are listed in Table S1. In
343 addition, the mechanisms of micro-explosion of miscible multi-component fuel droplet are
344 concluded and micro-explosion modes are proposed.
15
345

346 4.1. Effect of difference in boiling points of fuel components

347 Since the puffing and micro-explosion of miscible multi-component droplets are the
348 results of the first evaporation of light components, they are influenced by the difference in the
349 boiling points of fuel components [65, 66]. In fact, a greater difference in boiling points between
350 the components is favorable for occurrence of puffing and micro-explosion.

351 Han et al. [67] found that puffing or micro-explosion did not occur in the evaporation
352 process of dodecane/hexadecane blended droplets. This was because the difference of boiling
353 points between dodecane (218 ºC) and hexadecane (287 ºC) was too small (69 ºC). Won et al.
354 [68] also observed no puffing or micro-explosion in the evaporation process of n-heptane/n-
355 decane blended droplet due to the small difference in their boiling points (76.2 ºC). However,
356 Chow et al. [69] found that ethanol/palm biodiesel blended droplet (the difference in boiling
357 points was over 222 ºC) experienced bubble formation, growth and explosion, which shortened
358 the evaporation duration. Yang et al. [70] compared the evaporation processes of pure kerosene
359 and kerosene gel droplets. The boiling points of pure kerosene and gellant are 180-270 and
360 450 ℃, respectively. Compared with the small fluctuation in the diameter of pure kerosene
361 droplet, kerosene gel droplet exhibited a different evaporation process due to the larger
362 difference in boiling points (180-270 ℃), which was divided into three stages: kerosene
363 evaporation, gellant layer formation, and gellant layer swell and micro-explosion. There was a
364 gellant layer on the droplet surface to prevent fuel vapor from diffusing outside because the
365 mass diffusion rate of kerosene towards surface was lower than its evaporation rate on the
366 surface, leading to generation of many bubbles in the droplet. Then they accumulated, swelling
367 the droplet and thinning the gellant layer. Micro-explosion occurred when bubble pressure
368 exceeded the sum of surface tension of gellant layer and ambient pressure, resulting in the
369 breakup of droplet and further accelerating the droplet evaporation, as shown in Fig. 5.

16
370

371 Fig. 5. Comparison of the d2/d02 of kerosene and kerosene gel droplets [70].

372 Rao et al. [71] reported that the breakup probability of Jet A-1/butanol droplet was lower
373 than that of Jet A-1/ethanol droplet under the same conditions, indicating that a greater volatile
374 difference between components was favorable to nucleate and generate bubbles. Antonov and
375 Strizhak [72] believed that the mixing of different fuels could produce micro-explosion, which
376 greatly increased the droplet surface area. Moreover, Ma et al. [32] also confirmed that adding
377 light components into diesel caused micro-explosion and shortened droplet lifetime. They
378 explained that light components on the droplet surface evaporated first and then a thin layer of
379 heavy component was formed, which prevented the light component inside the droplet from
380 spreading out, causing its overheating to produce bubbles. Small bubbles gathered into large
381 bubbles and continued to grow. Eventually, the bubble burst when bubble pressure exceeded
382 the limit of the droplet, resulting in micro-explosion and higher droplet evaporation rate. This
383 agreed well with the results of Wang et al. [59] that the addition of ethanol into fatty acid methyl
384 ester (FAME) led to a slight micro-explosion, while pure FAME droplet evaporated smoothly.
385 Therefore, it is feasible to add light components into these fuels with poor evaporation (e.g.
386 heavy fuel oil[73]) to cause puffing and micro-explosion and thus to promote their evaporation.

387

17
388 4.2. Effect of ambient temperature

389 Similar to single-component fuel droplet, a higher ambient temperature increases the heat
390 supplied to the multi-component fuel droplet and thus accelerates it evaporation. The difference
391 is that ambient temperature also affects the nucleation of multi-component fuel droplet. It is
392 heterogeneous nucleation when the temperature is relatively low, resulting in a weak micro-
393 explosion. Homogeneous nucleation occurs under higher ambient temperature, which increases
394 the frequency of bubble formation and rupture, leading to a strong micro-explosion [45, 65] and
395 thus higher droplet evaporation rate.

396 The evaporation process of diesel blended with acetone-butanol-ethanol (ABE) droplet
397 was investigated by Ma et al. [32], as shown in Fig. 6. They found that the droplet evaporated
398 smoothly at 423 K because the light components inside the droplet had enough time to spread
399 to the droplet surface and evaporate when droplet temperature was low. At 623 K, however, the
400 light components inside the droplet were wrapped by a thin layer of heavy components and
401 were overheated to generate bubbles, leading to micro-explosion. The fluctuation of droplet
402 diameter at 823 K was faster and stronger, because higher ambient temperature increased the
403 heat diffusion inside the droplet, and the generation rate, movement and burst of bubbles. Wang
404 et al. [37] observed a puffing phenomenon in the evaporation process of jatropha straight
405 vegetable oil droplet at 673 K, during which the droplet diameter fluctuated slightly. At 873K,
406 droplet deformation, bubble formation and expansion, ejection and micro-explosion were
407 observed, causing more frequent and violent droplet diameter fluctuations, which increased
408 droplet evaporation rate and shortened droplet lifetime. Huang et al. [74] also reported that the
409 evaporation of biodiesel/propanol droplet was stable at 573 K, but micro-explosion occurred at
410 673 and 773 K. Micro-explosion was strengthened with the increase of ambient temperature,
411 which is similar to the results obtained by Meng et al. [75, 76]. It was believed that ambient
412 temperature was the main external factor that promoted micro-explosion. Han et al. [62]
413 reported that biodiesel/ABE droplet had fewer puffing times at 803 K than 1003 K in a nitrogen
414 atmosphere, resulting in fewer and smaller sub-droplets. Restrepo-Cano et al. [77] investigated
415 the evaporation behaviors of Arabian light crude oil droplet at 620, 710 and 840 K. The results
416 showed that the frequency of droplet break-up events increased with the ambient temperature,
417 while the intensity of break-up was smaller at higher temperature. It might because there was a
418 membrane on the droplet surface due to the preferential evaporation of light components at low
419 ambient temperature. This increased the surface tension and limited the mass diffusion, leading
420 to accumulation of light component vapor inside the droplet and thus strong micro-explosion.
18
421 However, both membrane formation and cracking reaction occurred at high temperature. The
422 latter decomposed the membrane and promoted the mass diffusion of light component, which
423 decreased the intensity of droplet micro-explosion.

424

425 Fig. 6. The evaporation processes of diesel-ABE blend droplets at different ambient
426 temperatures [32].

19
427 4.3. Effect of concentration of light component

428 The evaporation characteristics of biodiesel (BD) droplet mixed with n-propanol (P) at
429 ratios of 25%, 50%, and 75% at 673 K were studied by Huang et al. [74]. The results showed
430 that the micro-explosion of P25BD75 droplet occurred in the early stage of evaporation and had
431 the longest time and the highest intensity, while the micro-explosion of P75BD25 droplet
432 occurred in the latter stage of the evaporation. They concluded two conditions for the
433 occurrence of micro-explosion, i.e. overheating of light component inside the droplet and the
434 formation of an oil film on the droplet surface. When the concentration of light component was
435 small, it would quickly evaporate to form a heavy component oil film, leading to an early micro-
436 explosion. With the increase of light component concentration, generation rate of bubbles inside
437 the droplet enhanced and small bubbles coalesced to form larger ones, which strengthened
438 micro-explosion. When the concentration of light component was greater than that of heavy
439 component, the droplet diameter decreased rapidly due to the high content and fast evaporation
440 of light component, causing a later time for the internal heavy component to form an oil film.
441 At this time, significant light component has evaporated, resulting in a weaker micro-explosion.
442 Rosli et al. [78] compared diesel/gas-to-liquid (GTL) droplet in proportions of 20%, 50%, 80%,
443 and 100%. It was found that GTL50 droplet had the highest fluctuations in normalized diameter,
444 the strongest micro-explosion, the fastest evaporation rate, and the shortest lifetime. Han et al.
445 [62] studied biodiesel/ABE droplets with ABE proportions of 20%, 40%, 60%, and 80%. The
446 results showed that ABE60 droplet had the strongest micro-explosion, the fastest evaporation,
447 and the shortest lifetime. It was believed that the content of light components inside the droplet
448 when the oil film was formed determined the intensity of micro-explosion. ABE20 droplet did
449 not produce sub-droplets due to less light component, leading to less energy produced by bubble
450 burst. Coughlin and Hoxie [79] revealed that the strongest puffing occurred when
451 pentanol/soybean oil and butanol/soybean oil blended droplets had a 50%/50% mixing.

452 Table 3 summarizes the studies on the influence of light component concentration on the
453 evaporation characteristics of miscible multi-component droplet. It can be seen that there is an
454 optimal light component concentration. When the light component concentration is less than
455 the optimal value, droplet puffing and micro-explosion are promoted with the light component
456 concentration, leading to an improved evaporation. When the light component concentration is
457 higher than the optimal value, droplet puffing and micro-explosion are suppressed with the
458 increase of the light component concentration, causing a worsened droplet evaporation. It is

20
459 worth noting that droplet evaporation may be the best when the light component concentration
460 is around 50% due to the strongest puffing and micro-explosion [74, 78, 79].

461 Table 3. Effect of light component concentration on evaporation characteristics of miscible

462 multi-component fuel droplet.

Fuel Light component

Refs. Key results
components concentration
Increasing n-butanol concentration changed droplet
Xi et al. n-butanol + n- 10%-50% of n- nucleation from no to single and multiple bubbles, and
[50] hexadecane butanol evaporation from stable evaporation to partial breakup
and micro-explosion.
With the increase of ABE content, puffing frequency
Han et al. increased first and then decreased, and evaporation time
Diesel + ABE 10-80% of ABE
[66] decreased first and then increased. When ABE content
was 40%-50%, puffing was the strongest.
There was no puffing when ethanol was 10%. Many
nucleation sites were generated inside the droplet and
Syam et
Jet1 + ethanol 10-50% of ethanol continuous puffing occurred when ethanol was 30%.
al. [64]
Micro-explosion caused by puffing was the main
phenomenon when ethanol was 50%.
Increasing ethanol concentration decreased micro-
Wang et 10%-40% of
FAME + ethanol explosion delay time and droplet lifetime, and increased
al. [59] ethanol
micro-explosion intensity.

463

464 4.4. Micro-explosion modes of miscible multi-component fuel droplet

465 Fig. 7 illustrates the micro-explosion process of a miscible multi-component fuel droplet.
466 Shen et al. [80] pointed out that micro-explosion of miscible multi-component fuel droplet was
467 induced by vigorous bubble nucleation and rapid bubble growth of the light components.
468 Similarly, many researchers [52, 62, 70, 74] believed that the evaporation of light components
469 on the droplet surface leads to the formation of an oil film of heavy components [66], which
470 inhibits the outward diffusion and evaporation of light components inside the droplet. Then the
471 light components overheat and nucleate to produce bubbles when the droplet temperature is
472 higher than their boiling points. The pressure in the bubble increases with the continuous
473 evaporation of light components and bubble aggregation. Due to the pressure difference
474 between the inside and outside of the bubble and the flow in the droplet, the bubble moves
475 towards the edge of the droplet, stretching the oil film on the air-droplet interface and reducing
476 its surface tension [59]. Droplet micro-explosion occurs once the bubble pressure is higher than
477 the sum of surface tension of the thinnest part of oil film and ambient pressure. Rao et al. [81]

21
478 divided bubble growth into three periods. The first period was the growth of a single large
479 bubble with small bubbles coalescing. The second period was the growth of two or more large
480 bubbles merged by small bubbles, and the growth of larger bubbles coalesced by large bubbles.
481 In the third period, due to the bubble growth, droplet stretched in all directions, the oil film
482 thinned, and the droplet surface folded, resulting in Plateau-Rayleigh instability and capillary
483 wave propagation. Wang et al. [65] reported that the droplet always vibrated after generating
484 bubbles. They explained that it was due to rapid change of mass distribution in the droplet that
485 was attributed to the bubble movement and aggregation. Zhou et al. [82] reported that the
486 diameter of bubbles had a greater effect on micro-explosion than the number of bubbles. They
487 also agreed that bubble coalescence, growth and rupture caused micro-explosion. Meng et al.
488 [76] found that bubble position affected micro-explosion, and micro-explosion intensity was
489 high only when the bubble was located near the center. Faik and Zhang [83] also reported that
490 the micro-explosion caused by bubble rupture inside the droplet was more intense than the
491 micro-explosion on the droplet surface. In fact, the bubble takes a long time from generation to
492 rupture, so the bubble position tends to deviate from the center of the droplet before rupture,
493 leading to a relative small degree of droplet breakup. As a result, the micro-explosion process
494 of miscible multi-component droplet usually occurs repeatedly until the bubble formed by
495 evaporation of the remaining light components cannot break the oil film.

496 The bubbles can be released through the oil film with a little pressure when the surface
497 tension of oil film is small, so that large vapor bubbles cannot be accumulated inside the droplet,
498 resulting in a small degree of droplet breakup. Zhang et al. [52] proposed two evaporation
499 modes: surface and core modes. Surface mode meant that many micron-sized sub-droplets were
500 ejected from the droplet surface during the evaporation process, while the core mode meant that
501 there were many small bubbles inside the droplet. Due to the small surface tension of oil film,
502 larger bubbles formed by aggregation of many small bubbles were still relatively small, which
503 lead to local explosion of droplet, as shown in Fig. 8.

22
504

505 Fig. 7. Schematic diagram of micro-explosion of a miscible multi-component droplet.

506

507 Fig. 8. Schematic diagram of surface and core evaporation modes of a biodiesel-butanol
508 droplet [52].

509

510 5. Evaporation characteristics of liquid-liquid immiscible multi-component fuel droplets

511 Liquid-liquid immiscible multi-component fuel refers to a temporarily stable mixture of

512 two or more immiscible liquid components mixed by high speed stirring or ultrasonic under the
513 action of emulsifier, such as diesel-water and diesel-ethanol emulsified fuels. Their
514 microstructure is that one component is distributed in other continuous component in the form
515 of discrete droplets. Taking diesel-water as an example, there are two emulsion forms, i.e.
516 water-in-oil and oil-in-water, as shown in Fig. 9. Water-in-oil emulsified diesel has water as the
517 dispersed phase and pure diesel as the continuous phase, while oil-in-water emulsified diesel is
518 the opposite.

23
519
520 Fig. 9. Microstructures of diesel-water emulsified fuels.

521 The evaporation process of immiscible multi-component fuel droplet is similar to that of
522 miscible multi-component fuel droplet. There are also puffing and micro-explosion phenomena,
523 both of which are the result of the first evaporation of light components in the droplet due to
524 the difference in boiling points between components [51]. The evaporation characteristics of
525 diesel blended 10% ethanol droplet were studied by Han et al. [84]. They divided the droplet
526 evaporation process into three stages at 623 K: transient heating, fluctuation evaporation and
527 equilibrium evaporation. In the first stage, droplet expansion due to heat absorption was larger
528 than droplet contraction due to surface evaporation, causing the slow increase of droplet d2/d02
529 to the maximum value. In the second stage, the droplet diameter fluctuated because ethanol was
530 superheated and nucleated to produce bubbles, which continued to grow until the droplet
531 surface tension was overcome, leading to puffing and micro-explosion. The third stage was
532 mainly the evaporation of pure diesel, so the evaporation process roughly followed the d2 law.
533 When the temperature rose to 723 K, the fluctuation evaporation stage was more violent due to
534 the increase of heat supplied to the droplet by environment, resulting in a rapid increase of
535 bubble nucleation rate.

536 Kim et al. [85] divided the evaporation process of n-decane droplet mixed with 20% water
537 into three stages: droplet heating, droplet inflation/puffing and pure evaporation. In the droplet
538 heating stage, the d2/d02 of droplet increased first and then decreased since the droplet thermal
539 expansion rate was first larger and then less than the surface evaporation rate. In the droplet
540 inflation/puffing stage, water evaporation on droplet surface caused droplet puffing, while
541 water evaporation inside the droplet resulted in droplet inflation. As the temperature rose, the
542 droplet inflation gradually changed to puffing and the puffing probability increased. It was due
543 to the higher rate of water vapor production that enhanced bubble expansion and the lower
544 droplet surface tension that facilitated droplet breakup. Moreover, they also investigated the

24
545 impact of ambient pressure on droplet evaporation. The results reported that the generation and
546 growth of bubbles were inhibited by the pressure, because the boiling point of water increased
547 and some vapor dissolved in the droplet when ambient pressure was higher, leading to decreases
548 of probability and intensity of puffing. The pure evaporation stage was mainly the evaporation
549 of n-decane that followed d2 law. In addition, they found that ambient temperature had greater
550 influence on droplet evaporation rate and lifetime than ambient pressure. The probability and
551 strength of puffing increased with the temperature, which greatly improved droplet evaporation
552 rate and shortened droplet lifetime.

553 Since it promotes the generation of small droplets (<5 μm) and increases the evaporation
554 surface area, micro-explosion of immiscible multi-component droplet is the main reason for
555 faster droplet evaporation. Compared with other droplet secondary atomization technologies,
556 micro-explosion can obtain the smallest sub-droplet size and the largest evaporation surface
557 area ratio [86], which increases the spray volume and promotes spray evaporation [87].
558 Therefore, micro-explosion has attracted significant research attentions for liquid-liquid
559 immiscible multi-component fuel droplet. The studies on micro-explosion of liquid-liquid
560 immiscible multi-component fuel droplet are summarized in Table S2.

561 Different to miscible multi-component fuel droplet, immiscible multi-component fuel

562 droplet undergoes an aggregation process of dispersed phase before micro-explosion, which is
563 a key factor for the occurrence of micro-explosion [88]. The breakup characteristics of
564 kerosene/water emulsion droplet was studied by Watanabe et al. [89]. They reported that the
565 coalescence of dispersed water droplets led to the occurrence of micro-explosion and the droplet
566 color changed from milky white to transparent. Syed et al. [90] divided the micro-explosion
567 process of water-in-palm oil into four distinct stages. The first stage was emulsion separation,
568 in which the droplet shape did not change significantly but the color changed from milky white
569 to transparent. In the second stage, small water particles merged into larger ones, and some of
570 the unmerged water particles evaporated on the droplet surface, resulting in the occurrence of
571 puffing. The third stage was bubble growth, during which the merged water particles vaporized
572 to produce bubbles, leading to droplet expansion. In the fourth stage, bubbles burst which
573 caused droplet micro-explosion. Suzuki et al. [91] found that accelerating coalescence process
574 of dispersed water droplets increased the occurrence probability of micro-explosion by using
575 methylene blue to dye the water particles in the droplet. Table 4 summarizes the studies on the
576 internal parameters of emulsion droplet before micro-explosion. It can be seen that the
577 temperature of dispersed phase exceeds its boiling point before micro-explosion, meaning that
25
578 the dispersed phase has a certain level of superheat and metastable state. Therefore, more
579 aggregation of dispersed phase leads to larger dispersed droplets and superheat, whose
580 evaporation releases more energy and thus increases the occurrence probability and intensity of
581 micro-explosion [89, 92-94].

582 This section reviews the effect of various factors on micro-explosion of liquid-liquid
583 immiscible multi-component fuel droplet. Moreover, the mechanisms of micro-explosion of
584 liquid-liquid immiscible multi-component fuel droplet are concluded and micro-explosion
585 modes are proposed.

586 Table 4. Studies on internal parameters of emulsion droplet before micro-explosion.

Droplet
Refs. Research aims Key findings
components
Strizhak et N-tetradecane + Temperature until The temperature of water reached 100-125 ℃
al. [95] water micro-explosion before micro-explosion.
Oil/kerosene/ Temperature at phase interface before droplet
Explosive
Volkov and gasoline/waste breakup reached 100-125 °C; Temperature
disintegration of
Strizhak turbine oil/waste water emulsion
difference between phase interface and water
[96] transformer oil droplet center determined the number of sub-
droplets
+ water droplets after micro-explosion.
Maximum temperature of water droplets reached
Conditions of micro- ~130 ℃. Atomization (micro-explosion or
Moussa et N-tetradecane + explosion of puffing) was related to temperature, size and
al. [97] water emulsified fuel position of the trigger droplet. When one of
droplet these parameters was not optimal, it could be
compensated by the others.
Temperature and The threshold temperature and average
Antonov et Transformer oil
convection velocity convective velocity were 100-120 and 2.5-3
al. [98] + water
until micro-explosion mm/s before micro-explosion, respectively.

587

588 5.1. Effect of droplet size of dispersed phase

589 The size of dispersed phase affects its aggregation. The aggregation of the dispersed phase
590 is inhibited due to the high Laplace pressure when the diameter of dispersed phase is small. As
591 the diameter increases, the size distribution of dispersed phase inside the droplet becomes
592 heterogeneous, leading to a larger difference in Laplace pressure and a larger van der Waals
593 force between the dispersed phase [93]. This promotes the dispersed droplets to merge into
594 larger droplets [88, 99], thereby facilitating the occurrence of micro-explosion.

26
595 Califano et al. [100] showed that larger dispersed water droplets aggregated faster. They
596 believed that micro-explosion was related to phase separation and proposed two micro-
597 explosion modes. One was that larger water droplets formed by the aggregation of dispersed
598 water droplets evaporated to cause micro-explosion, and the other was that many small water
599 droplets evaporated simultaneously to cause micro-explosion. Ismael et al. [101] found that the
600 high pressure and shear flow of the emulsified fuel in the injection device led to smaller size of
601 dispersed phase, resulting in a decrease in aggregation of water droplets and postponing the
602 occurrence of micro-explosion. A higher injection pressure increased the micro-explosion delay
603 time. Shen et al. [93] also reported that the dispersed water droplets were more likely to
604 aggregate into large ones when their diameters increased, so that more water remained in the
605 droplet before micro-explosion. This increased the energy released by evaporation of water,
606 thus enhancing the probability of catastrophic micro-explosion of diesel/water emulsion droplet.
607 Mura et al. [102] showed that the number of sub-droplets generated by micro-explosion
608 increased first and then decreased with the increase of water droplet diameter in sunflower
609 oil/water droplet. It was believed that a higher degree of phase separation promoted micro-
610 explosion. Large water droplets exploded before phase separation occurred, while medium
611 water droplets had sufficient time for phase separation and water droplets aggregated into larger
612 ones by convection, causing stronger micro-explosion. For small water droplet, the phase
613 separation was limited by the energy required to overcome the pressure that the curved interface
614 exerted on the molecules inside the water droplet (Laplace pressure), resulting in a low degree
615 of phase separation. They also found that the temperature before micro-explosion with large,
616 medium and small water droplets was 95, 200 and 134 , respectively [99]. Droplet with
617 medium water droplets had the strongest micro-explosion due to the highest degree of superheat.
618 Therefore, there is an optimal dispersed phase size for micro-explosion. Micro-explosion is
619 strengthened with the increase of the dispersed phase size until the optimal size, and further
620 increase of dispersed phase size will weaken the micro-explosion.

621

622 5.2. Effect of dispersed phase and emulsifier concentrations

623 When preparation conditions of emulsion (i.e. stirring time and emulsifier content) are
624 unchanged, the size of the dispersed phase increases with its concentration. This accelerates the
625 aggregation of dispersed phase, thereby promoting the occurrence of micro-explosion.
626 However, if the concentration exceeds a certain value, the light dispersed phase will transform

27
627 into the continuous phase and the heavy continuous phase will transform into the dispersed
628 phase. Then the evaporation and diffusion of light components are not restrained, which makes
629 it difficult for micro-explosion to occur.

630 Shen et al. [93] found that the droplet only occurred puffing, a few small droplets were
631 ejected from the droplet surface and the entire droplet could not be broken when the water
632 content was 5%. These were attributed to low energy released by the evaporation of water. As
633 the water content increased, local micro-explosion occurred. When the water content was 20%,
634 the dispersed water droplets merged into a large one, whose explosive evaporation caused
635 catastrophic micro-explosion and produced many sub-droplets. The effect of ethanol
636 concentration on puffing and micro-explosion of ethanol/hexadecane droplet was investigated
637 by Shen et al. [80]. The results showed that the dispersed phase aggregated when the
638 concentration of ethanol was 20%. It evaporated quickly once the droplet temperature exceeded
639 the superheat limit of the dispersed phase, releasing abundant energy in a short time and causing
640 the droplet to explode violently. When the ethanol concentration was 40%, the degree of
641 aggregation of dispersed phase was decreased and puffing occurred. When the ethanol
642 concentration was 60%, n-hexadecane accumulated inside and ethanol surrounded the outside.
643 The ethanol evaporated first to satisfy the d2 law, and then the n-hexadecane evaporated. There
644 was weak puffing at the late stage of evaporation process, because a small amount of ethanol
645 was wrapped in n-hexadecane. Madan et al. [103] obtained similar conclusions from
646 experiments on the puffing and micro-explosion of diesel blended with ethanol droplets. They
647 reported that there was only puffing in most of the droplets when ethanol content was less than
648 10%. When ethanol content was 10%-40%, micro-explosion occurred and the droplet did not
649 expand before micro-explosion. No micro-explosion occurred when ethanol content was greater
650 than 40%.

651 The function of an emulsifier is to reduce the interfacial tension between the continuous
652 and dispersed phases, so that the dispersed phase can be stably distributed in the continuous
653 phase in the form of dispersed droplets. Hence, a higher emulsifier concentration increases
654 emulsion stability and reduces aggregation of dispersed phase and energy released by the
655 evaporation of dispersed phase, causing a change from micro-explosion to puffing [104]. The
656 impact of emulsifier content on puffing and micro-explosion characteristics of biodiesel/water
657 droplet was investigated by Khan et al. [105]. The results showed that 5% and 10% emulsifier
658 experienced micro-explosion while 15% emulsifier did not. A higher emulsifier concentration
659 decreased the size of dispersed phase and delayed the occurrence of micro-explosion [104, 106].
28
660 The puffing frequency increased as the size of dispersed phase decreased and the content of
661 emulsifier increased. This was consistent with the observation of Shen et al. [94] that puffing
662 and micro-explosion occurred at high and low emulsifier concentrations, respectively.

663

664 5.3. Effect of initial droplet size

665 Most of researchers found that there was no micro-explosion phenomenon in liquid-
666 liquid immiscible multi-component droplet when initial droplet size was relatively small. Khan
667 et al. [107] confirmed that the initial droplet diameter affected the frequency and delay time of
668 puffing and micro-explosion of diesel emulsified with water droplet and the size of the produced
669 sub-droplets. Watanabe et al. [89] reported that puffing and micro-explosion occurred when
670 initial droplet diameters were 0.7 and 1.2 mm, respectively. Kim et al. [85] observed no micro-
671 explosion in a small n-decane/water droplet (0.9 ± 0.1mm) because water evaporation was
672 completed before its aggregation. Fu et al. [108] suggested that emulsified fuels in real diesel
673 engines would not experience micro-explosion due to the very small droplets. However, Hsieh
674 et al. [92] reported that the droplet size had insignificant effect on the micro-explosion strength
675 of n-hexadecane/water droplet. They attributed it to the fact that there was only one water
676 droplet in the emulsion droplet. The change in droplet size would not significantly influence
677 the contact surface area between water droplet and n-hexadecane oil film, leading to little
678 impact of droplet size on the strength of micro-explosion. Therefore, for a droplet containing a
679 large amount of dispersed phase, the droplet size may have a significant effect on the occurrence
680 of micro-explosion and need to be further studied.

681

682 5.4. Effect of other factors

683 Other factors include ambient temperature, initial dispersed phase temperature, fluid
684 properties and impurities. The influence of heating temperature and fluid properties on micro-
685 explosion rate of emulsion droplet was studied by Moussa et al. [109]. The results showed that
686 micro-explosion rate enhanced with the ambient temperature. This was because the deactivation
687 of emulsifier accelerated phase separation under a high temperature, which enhanced the
688 aggregation of dispersed phase and thus promoted the occurrence of micro-explosion. In
689 addition, lower impurities and fuel viscosity resulted in higher micro-explosion rate. The
690 presence of impurities would reduce the level of metastable state of water droplets and a higher

29
691 viscosity increases the resistance of aggregation of water droplets, thereby inhibiting the
692 occurrence of micro-explosion. Shen et al. [93] found that the probability of micro-explosion
693 of diesel/water droplet increased with ambient temperature and catastrophic micro-explosion
694 gradually transformed to partial micro-explosion. This trend was related to the larger
695 temperature gradient in the droplet when ambient temperature was high, so the inner water
696 droplets did not evaporate when the surface water droplets evaporated, resulting in less energy
697 released by the micro-explosion. Antonov et al. [110] investigated the impact of initial water
698 core temperature on breakup of emulsion droplet. They reported that a lower initial temperature
699 increased the initial temperature difference between water core and combustible component,
700 shortened the micro-explosion delay time, and enhanced the strength of micro-explosion. If the
701 initial temperature was reduced from 353 to 273 K, the average size of the sub-droplets was
702 reduced by 80% to 90%.

703

704 5.5. Micro-explosion modes

705 Existing studies showed that micro-explosion of liquid-liquid immiscible multi-

706 component droplet had two modes, namely instantaneous and bubble micro-explosion modes.
707 For the instantaneous micro-explosion mode, dispersed small droplets of light component
708 aggregate to form one larger droplet. When the temperature exceeds the overheating limit of
709 light component, the light component evaporates instantaneously and the released energy
710 breaks droplet completely [80], as illustrated in Fig. 10. In this mode, there is no expansion
711 before micro-explosion and micro-explosion occurs in a very short time. After a micro-
712 explosion, there is almost no droplet left. The number of produced sub-droplets is large and the
713 size is small, which is more conducive for rapid droplet evaporation to form a uniform mixture,
714 thereby improving engine performance.

715
716 Fig. 10. Schematic diagram of instantaneous micro-explosion of a liquid-liquid immiscible
30
717 multi-component droplet.

718 For the bubble micro-explosion mode, the light component evaporates inside the droplet
719 to generate bubbles when the energy released by the instantaneous evaporation of the
720 aggregated light component is insufficient to break the droplet (e.g. aggregation is relatively
721 small or droplet surface tension is large) [101]. As shown in Fig. 11, the bubble ruptures and
722 the micro-explosion occurs when the bubble gradually grows to a point where the bubble
723 pressure is larger than the sum of droplet surface tension and ambient pressure, which is similar
724 to the micro-explosion of miscible multi-component droplet. Swelling is observed before
725 micro-explosion. The intensity of micro-explosion depends on the bubble position. Zhang et al.
726 [111] reported that droplet only experienced puffing and partial micro-explosion when the
727 bubble was close to droplet surface, while overall micro-explosion occurred when the bubble
728 was located in the droplet center. Since it takes a long time from bubble generation to rupture,
729 the degree of droplet breakup is relatively small compared to instantaneous micro-explosion.
730 Therefore, the micro-explosion process tends to repeat until the bubble formed by dispersed
731 phase cannot break the droplet.

732
733 Fig. 11. Schematic diagram of bubble micro-explosion of a liquid-liquid immiscible multi-
734 component droplet.

735

736 6. Evaporation characteristics of liquid-solid immiscible multi-component fuel droplets

737 With the development of technology in recent years, it is possible to produce nanoparticles
738 with special properties. These particles are mostly metal with sizes between 10-100 nm and
739 have high energy release rate and oxidation heat. Adding them to liquid fuel in a certain
740 proportion to form a nanofluid fuel can improve the fuel thermal physical properties, including
741 volumetric energy density and evaporation rate, which can shorten the ignition delay and

31
742 thereby increase the combustion and heat release rates. Meanwhile, it can also reduce pollutant
743 emissions [112]. Hence, many researchers have experimentally investigated the evaporation
744 characteristics of nanofluid fuels to obtain the optimal conditions that promote evaporation
745 when using nanoparticles. On the one hand, nanoparticles absorb thermal radiation [113], which
746 improves the heat transfer inside the droplet and accelerates evaporation [114, 115]. On the
747 other hand, the accumulation of particles on droplet surface reduces its evaporation rate [116].
748 It is worth noting that nanoparticles can also cause micro-explosion [117], leading to droplet
749 breakup and promoting the evaporation. The evaporation process of nanofluid fuel droplet is a
750 result of the combined effect of the three mechanisms mentioned above.

751 This section discusses the effect of different factors on the evaporation characteristics of
752 nanofluid fuel droplets. The related studies are summarized in Table S3. In addition, the
753 mechanisms and modes of micro-explosion of nanofluid fuel droplets are also discussed.

754

755 6.1. Effect of ambient temperature and nanoparticle concentration

756 Ambient temperature is a decisive factor affecting the micro-explosion of nanofluid fuel
757 droplet. When the temperature is relatively low, the droplet evaporates smoothly and there is
758 no micro-explosion. However, micro-explosion occurs when the temperature is relatively high,
759 which facilitates the evaporation of droplet. Nanoparticles concentration affects the competitive
760 relationship between the absorption of thermal radiation and the particle aggregation. The
761 former dominates when the particle concentration is relatively low, resulting in the
762 enhancement of droplet evaporation rate. The latter plays a dominant role when particle
763 concentration is relatively high, leading to lower droplet evaporation rate. The concentration of
764 nanoparticles also influences the micro-explosion process.

765 The evaporation characteristics of diesel droplet with different ceria concentrations
766 (0.05%-5%) at 673 and 873 K was studied by Wang et al. [118]. They found that the droplet
767 evaporation process was divided into transient heating and equilibrium evaporation at 673 K.
768 The lifetime of nanofluid droplet was longer than that of pure diesel, because the aggregation
769 of nanoparticles formed a porous spherical shell that inhibited fuel evaporation. However, the
770 droplet evaporation process at 873 K was divided into three stages, namely transient heating,
771 fluctuation evaporation and equilibrium evaporation. There was micro-explosion which broke
772 the particle aggregation and increased the droplet evaporation surface area. Consequently,

32
773 droplet evaporation rate was improved and droplet lifetime was reduced [63]. Wang et al. [118]
774 also reported that there was an optimal particle concentration for droplet evaporation.

775 Gan and Qiao [119] reported that droplet evaporation deviated more obviously from the
776 d2 law without micro-explosion under the condition of high particle concentration, low ambient
777 temperature, weak convection and high boiling point of the fuel. They believed that this was
778 the result of the aggregation of particles in the droplet. If the particle aggregation time was
779 shorter than or equal to the droplet lifetime, larger aggregates would be formed in the droplet
780 evaporation process, which inhibited the diffusion and evaporation of fuel components, thereby
781 reducing the evaporation rate. If the aggregation time was longer than the droplet lifetime, the
782 particle aggregates were smaller and had less impact on droplet evaporation. However, there
783 was no deviation of evaporation from the d2 law under conditions that were conducive to reduce
784 droplet lifetime. Javed et al. [54] reported that micro-explosion occurred at the late evaporation
785 stage of kerosene droplet added with ligand-protected aluminum nanoparticles at 973 K, which
786 accelerated the evaporation. A higher nanoparticles concentration advanced the micro-
787 explosion time. When the temperature was higher than the melting point of particles at 1073 K,
788 some particles gathered on the droplet surface melted, which supplied additional heat of fusion
789 to the droplet and greatly enhanced the evaporation rate.

790 Tanvir et al. [113] reported that the evaporation rate of ethanol droplet with graphite
791 nanoparticles was higher than that of pure ethanol droplet in the early evaporation stage, but
792 lower in the late evaporation stage. It may be due to fact that the absorption of radiation energy
793 of particles dominated in the early evaporation stage, while particle aggregation was dominant
794 in the late evaporation stage that reduced the effective evaporation surface area. The
795 evaporation characteristics of jatropha vegetable oil/diesel droplet with a low particle
796 concentration at the level of ppm at 873 K were studied by Wang et al. [120]. The results showed
797 that no micro-explosion occurred and there was an optimal particle concentration for facilitating
798 droplet evaporation. They suggested that nanoparticles at a ppm level was better than a
799 percentile level in enhancing droplet evaporation. Although the droplet with the percentile level
800 of particle concentration could experience micro-explosion, the particles inside the droplet
801 aggregated to form a spherical shell in the later stage of evaporation, which suppressed the
802 droplet evaporation. Wang et al. [36] found that the average droplet evaporation rate of diesel
803 droplet with cerium oxide nanoparticles was enhanced as particle concentration increased from
804 0.05% to 0.25% at 873 K. The micro-explosion delay time was reduced by 24.1% and 47.1%,
805 and the micro-explosion intensity was increased by 37.5% and 49.5%, respectively when
33
806 compared to diesel. However, the evaporation rate in the steady evaporation stage was reduced
807 due to particle aggregation. The results reported in Wang et al. [117] and Ferrão et al. [121] also
808 demonstrated that intensity of droplet micro-explosion became larger with the increase of
809 nanoparticles concentration. This could be explained by the reason that increasing particle
810 concentration strengthened the heterogeneous nucleation, which generated more bubbles [36].

811

812 6.2. Effect of other factors

813 There are also other factors affecting the evaporation characteristics of nanofluid fuel
814 droplet, such as surfactant, type, size and shape of particle. The influence of surfactant on the
815 evaporation of heptane droplet with the addition of aluminum nanoparticles was investigated
816 by Javed et al. [55]. They reported that surfactant formed a thin layer on droplet surface at low
817 temperatures, which retarded the diffusion of fuel components. When nanoparticles were added,
818 there was a thick and porous shell on the droplet surface due to accumulation of particles bonded
819 with adsorbed surfactant, which further inhibited the droplet evaporation. However, it was
820 difficult to form a dense and porous shell at high temperature as a result of decomposition of
821 surfactant. The depression of fuel diffusion was weakened, which thus improved the
822 evaporation rate. The impact of particle type on the evaporation of deionized water droplet was
823 studied by Chen et al. [122]. The results showed that droplet evaporation with 0.05% Ag
824 nanoparticles and 1% surfactant was larger than that of pure deionized water droplet. However,
825 droplet evaporation with 0.05% Fe2O3 nanoparticles and 1% surfactant was smaller than that of
826 pure deionized water droplet. This may be because the ability to absorb radiation is different
827 for different particles, so that the competitive relationship between promoting and inhibiting
828 effects of particles on evaporation was changed. Ghamari and Ratner [114] studied the impact
829 of carbon shape (nanoparticles, nanotubes and nanoplatelets) on the evaporation of aviation fuel.
830 They reported that carbon nanotubes had the best effect on promoting droplet evaporation.
831 Ferrão et al. [121] found that the size of aluminum nanoparticles had insignificant effect on
832 droplet lifetime and micro-explosion strength of hydro-processed vegetable oil.

833

834 6.3. Micro-explosion modes

835 Table 5 summarizes the mechanisms of micro-explosion of nanofluid fuel droplet. Micro-
836 explosion of nanofluid fuel droplet is caused by the rupture of bubbles generated inside the

34
837 droplet, which is the same as the micro-explosion of miscible multi-component fuel droplet.
838 However, the sources of bubbles are different. There are two bubble sources in the nanofluid
839 fuel droplet. The first one is from the evaporation of light components, and the other is produced
840 by heterogeneous nucleation sites due to the heating of nanoparticles on the surrounding fluid.
841 Small bubbles merge into larger ones under the van der Waals force, surface tension and droplet
842 internal flow. The bubble bursts once the bubble pressure is larger than the sum of droplet
843 surface tension and ambient pressure, leading to the distortion and breakup of the droplet, as
844 shown in Fig. 12.

845 Table 5. Mechanisms of micro-explosion of nanofluid fuel droplet.

Droplet
Refs. Nanoparticles Mechanisms of micro-explosion
components
Heterogeneous nucleation sites were formed by
temperature of aluminum nanoparticles exceeding the
Javed et al.
kerosene Aluminum boiling point of kerosene and evaporation of overheated
[54]
light components, leading to bubble burst and micro-
explosion.
Bubble rupture was produced by heterogeneous nucleation
Wang et al. sites that were formed by nanoparticles’ heating on
Diesel Ceria
[118] surrounding liquid and the evaporation of light
components, leading to micro-explosion.
The burst of bubble produced by heterogeneous nucleation
Dai et al.
Diesel Cerium oxide sites and evaporation of light components led to micro-
[123]
explosion.
The temperature of nanoparticles was higher than the
Wang et al. liquid temperature, which formed a local hot spot and
Diesel Cerium oxide
[36] became a heterogeneous nucleation site to generate
bubbles. The burst of bubbles caused micro-explosion.
Hydro-
Particles accumulated on droplet surface formed a local
Ferrão et processed
Aluminum hot spot, which induced nucleation to produce bubbles.
al. [121] vegetable
The rupture of bubbles caused micro-explosion.
oil

846
847 Fig. 12. Schematic diagram of micro-explosion of a nanofluid fuel droplet.

35
848

849 7. Challenges and future research directions

850 In spite of significant experimental investigations on the evaporation characteristics of fuel

851 droplets, there are still many research gaps that should be addressed, which are concluded as
852 follows:

853 • All current experimental methods for fuel droplets have their own disadvantages, as
854 discussed in section 2. Therefore, researchers have to choose a relatively appropriate
855 method according to their research purposes. In the case that existing methods are difficult
856 to improve, advanced numerical methods are needed to eliminate the effect of external
857 conditions on droplet evaporation.
858 • The tested droplet size is generally at the millimeter level, while the spray droplet size in
859 real engines is at the micrometer level. Thus the evaporation characteristics of the fuel
860 droplets may be different. However, the preparation and measurement of an isolated micron
861 droplet is very difficult, which could be evaporated very quickly (within 50 ms) [65].
862 Therefore, advanced simulation methods are needed to investigate evaporation
863 characteristics of micron droplets. To achieve this, the experimental data on evaporation
864 characteristics of millimeter droplets are very valuable for verifying and optimizing the
865 numerical models.
866 • Most of the experiments on multi-component fuel droplet evaporation were conducted
867 under atmospheric pressure and static conditions. For in-cylinder direct injection engines,
868 fuel is generally injected at the end of the compression stroke when the pressure is higher
869 than atmospheric pressure and the ambient gas is turbulent, which may cause different
870 droplet evaporation characteristics. Future studies are needed to investigate droplet
871 evaporation under elevated pressure and turbulent conditions.
872 • Due to experimental limitations, there is a lack of studies on droplet internal behavior. The
873 microscopic mechanism of droplet evaporation has not been clearly understood. There are
874 few studies on the effect of initial size of multi-component fuel droplet on micro-explosion.
875 However, there is no consensus in the existing studies, which needs further investigations.
876 • Current studies only concerned one droplet in isolation, but did not combine it with jet
877 spray research. Optimizing fuel spray and combustion based on the evaporation
878 characteristics of fuel droplets can provide useful guidance for better fuel utilization in real
879 engines.

36
880

881 8. Conclusions

882 Investigating the evaporation characteristics of a fuel droplet is of great significance for a
883 cleaner and more efficient use of fuels in engines. This paper critically reviews the current
884 experimental studies on the evaporation characteristics of a fuel droplet in different fuel
885 components. The major conclusions are summarized as follows:

886 (1) There are three research methods for fuel droplet evaporation, including suspension, flying
887 drop and levitation. Each method has its own advantages and disadvantages, leading to
888 different applications. Among them, suspension and levitation methods are the most widely
889 applied due to their simple setups and convenient measurements.

890 (2) The evaporation process of a single-component fuel droplet is divided into two stages:
891 transient heating and equilibrium evaporation. Droplet evaporation are affected by the fuel
892 boiling point, latent heat of evaporation and other physical and chemical properties (e.g.
893 mass diffusivity). The droplet evaporation rate increases with the initial droplet diameter
894 and droplet lifetime increases with the ambient pressure. Turbulence promotes droplet
895 evaporation, but the degree of impact is weakened with the increase of turbulence intensity.

896 (3) There are puffing and micro-explosion phenomena in the evaporation process of miscible
897 multi-component fuel droplet, which breaks up the droplet to increase the evaporation
898 surface area and thus the droplet evaporation. A larger difference in the boiling points of
899 components and a higher ambient temperature are favorable for puffing and micro-
900 explosion, thereby improving the droplet evaporation. There is an optimal concentration of
901 light component at around 50% for droplet evaporation.

902 (4) Liquid-liquid immiscible multi-component droplet also has puffing and micro-explosion
903 phenomena that promote droplet evaporation. The micro-explosion is related to the
904 aggregation and superheat of dispersed phase. Greater aggregation and overheat increase
905 the probability and intensity of micro-explosion. There is an optimal size and concentration
906 of dispersed phase for micro-explosion. Increasing the emulsifier concentration and fluid
907 viscosity reduce the probability of micro-explosion. Reducing impurities and initial
908 temperature of the dispersed phase are conducive to the occurrence of micro-explosion.
909 The initial droplet size may have an effect on micro-explosion, which needs a further
910 research.

37
911 (5) Nanoparticles could either enhance or reduce the evaporation of liquid-solid immiscible
912 multi-component fuel droplet, which are determined by their materials, shape, and
913 concentrations. Nanoparticles with a stronger ability to absorb heat radiation may facilitate
914 droplet evaporation, while the effect of particle size is not obvious. There is an optimal
915 concentration of nanoparticles for droplet evaporation.

916 (6) Future studies need to develop more advanced experimental and numerical methods to study
917 droplet evaporation and its internal behavior under real engine conditions. Meanwhile,
918 studies on fuel droplet evaporation should be combined with fuel spray and combustion to
919 provide guidance for improving engine performance.

920

921 Declaration of Competing Interest

922 The authors declare that they have no known competing financial interests or personal
923 relationships that could have appeared to influence the work reported in this paper.

924

925 Supplementary Information

926 Additional information about evaporation of miscible multi-component fuel droplets

927 (Table S1), micro-explosion of liquid-liquid immiscible multi-component fuel droplets (Table
928 S2), and evaporation of nanofluid fuel droplets (Table S3).

929

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