Journal of Food Engineering 114 (2013) 2228

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Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

An improvement in the immersion freezing process for frozen dough via ultrasound irradiation
Song-Qing Hu a,c, Guang Liu c, Lin Li a,c, Zhi-Xin Li c, Yi Hou b,c,
a

Guangdong Province Key Laboratory for Green Processing of Natural Products and Product Safety, South China University of Technology, Guangzhou, Guangdong 510640, China State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, Guangdong 510640, China c College of Light Industry and Food Sciences, South China University of Technology, Guangzhou, Guangdong 510641, China
b

a r t i c l e

i n f o

a b s t r a c t
The ultrasound-assisted freezing (UAF) process, the inuence of UAF on the quality and microstructure of frozen dough, were investigated. Dough cylinders were immersion frozen in an ultrasonic bath with 25 kHz frequency and ve different power levels. The results showed that UAF process was consists of three stages: a liquid-state temperature decrease stage, a phase-transition stage, and a solid-state temperature decrease stage; ultrasound enhanced heat transfer more efciently in the latter two stages than in the rst stage, due to more heat generation in the rst stage. At 288 or 360 W power levels, the total time for dough freezing shortened more than 11% signicantly (P < 0.05), and the required time for each stage was reduced. Moreover, crystal nucleation was also enhanced by ultrasound with the formation of a large number of tiny ice crystals inside the frozen dough, and the maximum penetration force of ultrasound-assisted frozen dough increased. 2012 Elsevier Ltd. All rights reserved.

Article history: Received 11 April 2011 Received in revised form 25 July 2012 Accepted 29 July 2012 Available online 8 August 2012 Keywords: Ultrasound-assisted freezing Heat transfer Dough Nucleation Heat generation

1. Introduction The expansion pressures generated by the large ice crystals which are formed during food-freezing and freezing-storage processes may damage the food structure and lead to a deterioration in the structure of the frozen food (Inoue et al., 1994; Rasanen et al., 1995). Presently, efforts, such as shortening the freezing period, increasing the freezing rate and maintaining temperature stability during freeze-storage, are being made to optimize important factors that diminish the inuence of large ice crystals on food quality. New techniques have been developed in food freezing, such as high-pressure food freezing (Fuchigami et al., 1998), application of ice nucleation active bacteria (Li and Sun, 2002a; Widehem and Cochet, 2003), biological freezing protein technique (Zasypkin and Lee, 1999), Cell Alive System (CAS) technology (http://www.a-interview.com/en/world/item/92.html), superchilling technology (Kaale et al., 2011), and ultrasound-assisted food freezing (Zheng and Sun, 2006). Power ultrasound, with high energy and low frequency in the kHz range, can exert ultrasonic cavitation, mechanical and thermal

Abbreviations: BU, Brabender units; FTA, food texture analysis; SEM, scanning electron microscopy; UAF, Ultrasound-assisted freezing. Corresponding author at: College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510641, China. Tel.: +86 20 8711 2614x27; fax: +86 20 8711 3840. E-mail addresses: ceyhou@scut.edu.cn, fesqhu@scut.edu.cn (Y. Hou). 0260-8774/$ - see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jfoodeng.2012.07.033

effects on chemical and structure make-up of the food, as well as cause a series of secondary effects, such as shock waves and micro-jets. Utilization of power ultrasound in food processing, preservation and extraction is a green novel technology (Chemat et al., 2011). Ultrasound-assisted freezing (UAF) can improve the quality of frozen food without the need for additional additives, which is in line with the developing trend in the modern green food industry, and it could have promising applications in freezing of foods (Kiani et al., 2012; Saclier et al., 2010). Ultrasound cavitation can induce primary ice nucleation by the cavitation bubble collapses or movements, and promote secondary ice nucleation by breaking up the pre-existing dendritic ice crystals into smaller fragments to produce the smaller crystals with greater size uniformity (Chow et al., 2003, 2004, 2005; Delgado et al., 2009; Delgado and Sun, 2011; Inada et al., 2001; Kiani et al., 2011, 2012; Petzold and Aguilera, 2009; Saclier et al., 2010; Zhang et al., 2001, 2003; Zheng and Sun, 2006), so that the quality of frozen food can be improved during the UAF process. It has been reported that freezing under the ultrasound irradiation at 25 kHz frequency did less damage to potato cells and facilitated a better preservation of cell structure in comparison with traditional food-freezing techniques (Li and Sun, 2002b; Zheng and Sun, 2006). Microstructures with small and uniform ice crystals have been determined in ultrasound-assisted frozen wet gluten to benecially reduce the deterioration of the gluten network and improve its quality (Song et al., 2009). Although power ultrasound was recognized to enhance convection of heat transfer by acoustic cavitation or acoustic streaming (Legay

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et al., 2011), these previous studies have focused mostly on the impacts of ultrasound on ice crystallization with little attention to the heat-transfer effect during the UAF process. In this paper dough was used as the experimental material to investigate the inuence of ultrasound on freezing efciency because of the extensive use in the food industry and easy moldition into a uniform shape which can eliminate the interference of food shape in the experiments. Dough cylinders were immersion frozen in an ultrasonic bath system, in which ultrasound was applied intermittently with 30 s on/30 s off duty cycle at 25 kHz frequency and at ve different power levels (175-, 224-, 288-, 360-, or 418W). The properties of ultrasound-assisted frozen dough were monitored via food texture analysis (FTA). 2. Materials and methods 2.1. Wheat our processing High-grade bread our (Guangdong Baiyan Grain and Oil Industrial Co., Ltd., Guangzhou, China) was used in this study. The protein and moisture contents of this our were measured with the results of 13.3% protein content and 13.2% moisture using the Dumas combustion method [Nitrogen Autoanalyzer (Tru Spec N, LECO, USA)] and HB4-3 rapid water content determination (Mettler-Toledo, Switzerland) respectively. A 300 g kneading-through (mixer) was used for the our farinograph (Brabender OHG, Duisberg, Germany). According to AACC approved method 5421 (AACC, 1984), 297.2 g of the our samples were used to determine the attributes and prepare dough sample. The main attributes of the our determined by the farinograph are 3.1 min of arrival time, 67% arrival time absorption at 500 BU (Brabender units), 14.4 min of departure time, 11.3 min of stability time, 11.2 min of peak time, and 34 BU mixing tolerance index. Water was added to the our until the moisture content reached 67% with the total dough weight of 781 g; no other ingredient was added, and the sample was mixed at 25 C and was kneaded at a speed of 63 2 r/min for 11.2 min before being rolled and shaped. 2.2. The UAF system An ultrasonic bath system (Song et al., 2009) was used for dough immersion freezing assisted with ultrasound with a 50% (v/v) glycol (AR, the Chemical Reagent Factory, Tianjin, China) water solution as the coolant. The ultrasonic equipment with 25 kHz frequency was fabricated to meet our specications with tunable electric power at the range of 0450 W, and the coefcient of electric energy converting to ultrasonic energy was approximately 90%. Piezoelectric ceramic transducers were attached to the center of the bottom of the ultrasonic tank to facilitate a uniform and steady ultrasonic irradiation throughout the dough sample. 2.3. The UAF process In total, 750 g of dough was weighed and molded into a cylinder with 76 mm diameter and 140 mm height. The shaped dough was put into a synthetic glass cylinder with a radius of 76 mm, and the dough was tightly attached to the cylinder wall. The bottom of the dough was aligned with the cylinder bottom such that it could be tightly sealed via a Paralm membrane. Before the UAF process, the temperature of the dough should be balanced to 25 1 C for several hours. The sealed samples were immersed in a 20 C coolant. To avoid uctuations of velocity in the uid and the intensity of the ultrasound due to different positions in the ultrasound tank, all of the samples were specically placed at the same position for

each experiment. The real-time temperature at the geometric center of each sample (i.e., the sample temperature) was measured via a T-type thermocouple, which connected to Digi-Sense 12 Channel Scanning Benchtop Thermometer, 115 VAC produced by ColeParmer Instrument Corporation. The sample temperatures were acquired at 1 min interval and transmitted to a computer to obtain the freezing curves. In the UAF trials, the samples were irradiated by ultrasound waves with the following conditions: 25 kHz frequency, 30 s on/30 s off duty cycle, and 0, 175, 224, 288, 360, or 418 W power levels. The freezing process ended as soon as the temperature of each sample reached 18 C. After freezing, each sample was placed into a double high-density polyethylene bag and stored at 20 1 C which was the same temperature of coolant. Each freezing experiment was repeated in triplicate. 2.4. Scanning electron microscopy A thin-diameter freezing dough rod (15 mm diameter and 100 mm height) was prepared with UAF processing, and after one week of freeze-storage, the rod was placed in liquid nitrogen for several minutes to make it easily fractured without distortion of the shape and the distribution of ice crystals in the frozen dough as a result of thin-diameter, and then the fractured rod was freezedried in a freeze-dryer Model ALPHA 1-4 (Christ Co., Germany) to prepare for the scanning electron microscopy (SEM) analysis (LEO 1530 VP scanning electron microscope (LEO Co., Germany). The angular void on the fracture face of the dried rod in the SEM image reects the size and distribution of ice crystals in the frozen dough prepared by UAF process, whereas the larger spherical voids in the SEM image were interpreted to be the gas bubbles that were formed during dough kneading (Zounis et al., 2002a, 2002b). The fracture surface of the thin-diameter freezing dough rod was sampled, and its bottom was xed on the stage of a LEO 1530 VP scanning electron microscope (LEO Co., Germany) with conductive, double-sided adhesive tape. Gold preprocessing was performed under vacuum conditions prior to being observed under SEM. The SEM images of the samples were digitally captured at different locations at a 100 magnication. 2.5. FTA test for frozen dough Samples that were frozen under either ultrasonic irradiation or conventional immersion freezing were analyzed using a TA-XY2 food texture analyzer (Stable Micro Systems, U.K.). After immersion freezing and freeze storage at 20 1 C for one week, 50 g of the freezing dough was thawed under constant temperature (23 2 C) and relative humidity (60 5%), and this specimen was rolled out into a 1-mm-thick frozen dough wafer on a sheeter. A 0.75-S glass, spherical FTA probe was employed to penetrate the frozen dough wafers at a xed velocity, and the maximum penetration distance and penetration force of the frozen dough wafers were obtained based on the curve of the wafers stress as a function of time. The values that are reported herein are the average of three replicated measurements. 2.6. GCMS analysis on frozen dough The volatile compounds in the frozen dough were extracted and determined by solid-phase micro-extraction-gas chromatography mass spectrometry (SPMEGCMS). The compounds were extracted from 5 g frozen dough by SPME using a 65 lm polydimethylsiloxane-Carboxen ber (Supelco, USA) for 1 h at 60 C in a water bath, and then the extracted compounds were introduced directly into the injector of the GCMS (Thermo sher, USA) for desorption at 250 C for 3 min in the splitless mode to be separated and analyzed with a fused silica coated column DB-

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5MS (0.20 mm 25 m 0.25 lm). Helium was used as carrier gas with the velocity of 0.8 ml/min. The oven was initially kept at 40 C for 3.5 min, and then was heated at the rate of 5 C/min to 90 C, and then was continuously heated at the rate of 12 C/min to the nal temperature 220 C, and then maintained at the nal temperature for 7 min, and the mass spectroscopy works at the conditions of ionization energy 70 eV, mass range m/z 33495. 2.7. Statistical analysis Signicant differences in the treatments due to the application of ultrasound were assessed using the SPSS software package (SPSS, Chicago, IL, USA, Version 12.0.2, 2004) at 95% signicance level. 3. Results and discussion 3.1. The dough freezing curves The dough-center temperatures as a function of freezing time under the UAF processing at 360 W power level are depicted in Fig. 1. Similar to immersion freezing without ultrasound, the UAF process also consists of three stages: a liquid-state temperature decrease stage (>0 C), a phase transition stage (0 to 3 C) and a solid-state temperature decrease stage (<3 C). There were many complex solutions inside dough sample as a result of components dissolvation and the properties of these solutions could change with the water freezing, so the equilibrium freezing temperature decreases from 0 C to 3 C in the experiments. Because there was a temperature gradient from the center to the surface within the dough during the freezing process, the aforementioned stages that had been divided according to the temperature at the geometric center of the dough sample could not represent the state of the entire dough sample; nonetheless, it was useful in analyzing ultrasound-assisted dough freezing. As shown in Fig. 1, comparing the UAF with the conventional immersion freezing, it can be observed that the time which each stage needs decrease notably as a result of enhancement of the ice nucleation and heat transfer by the ultrasound treatment. There are three kinds of mechanism of ultrasound induces primary nucleation (Saclier et al., 2010; Kiani et al., 2011). Firstly, the high pressures occurring during the vigorous collapse of transient ultrasonic cavitation bubbles results in high degrees of supercooling. Secondly, the micro-streaming caused by the movement of stable ultrasonic cavitation bubbles may also induce ice nucleation. Thirdly, the concentration and agglomeration of ice cluster near

the cavitation bubble is another approach proposed for inducing nucleation. Furthermore, ultrasonic cavitation promote the secondary nucleation of ice, the pre-existing dendritic ice crystals can be broken into crystal fragments as ice nucleus (Delgado et al., 2009; Petzold and Aguilera, 2009; Chow et al., 2003, 2004, 2005). Ultrasound may have powerful macroscopic effects for the enhancement of convection heat transfer (Legay et al., 2011). Dough is a heterogeneous system with the coexist of solid (gluten and starch) and uid where many compounds dissolve in. Two phenomena, acoustic cavitation and acoustic streaming, arise from the propagation of power ultrasonic waves into a uid, may cause macroscopic turbulent ows and the high-speed collision of microscopic particles to make the solidliquid boundaries thinner and the heat-transfer resistance decreased (Feng and Li, 1992). The improvement of heat transfer during the dough-freezing process by ultrasound can also shorten the freezing time for each stage. 3.2. The effects of electrical power on freezing time To compare freezing times under different conditions, in Fig. 1 the initial and nal temperatures were unied for the freezing process as the liquid-state temperature decrease stage (23.50 C), the phase transition stage (0  3 C) and the solid-state temperature decrease stage (3  17 C). Total times for UAF at various ultrasound irradiation power levels of 175, 224, 288, 360, and 418 W were present in Fig. 2. The total time for each UAF process (except for the case of 175 W power level) is shorter than that of conventional immersion freezing (the control group in Fig. 2), and the results showed clearly that dough freezing was improved by ultrasound irradiation. Three effects, inducing nucleation, heat transfer enhancement, and heat generation (thermal effect), arises from the propagation of ultrasonic waves into the dough. Nucleation and heat transfer enhancement would improve the freezing rate but the effect of heat generation is adverse to it resulting from an increase in the heat-transfer load during freezing which would be unfavorable with respect to dough freezing, and the magnitude of these three effects depends on the power level of ultrasound closely and complexly. So if the effects of inducing nucleation and heat transfer enhancement were less than the effect of heat generation, such as at 175 W power level, as a result the total freezing time was longer than that of the conventional freezing. But at 224, 288, 360, and 418 power levels, the effects of inducing nucleation and

180

30 without ultrasound 23.5 20 with ultrasound

170

160

temperature /

10

Time / min
0 -3 -17

150

140

-10

130

-20 0 20 40 60 80 100 120 140 160

120 control 175W 224W 288W 360W 418W

Freezing time / min

Fig. 1. The dough-freezing curves during the UAF process at 360 W power level and the conventional immersion freezing process.

Electrical power of ultrasound / W

Fig. 2. The total required time for dough freezing under ultrasound at different power levels. Mean values standard deviation of three replicated measurements.

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25

80

70

Temperature decrease in liquid-state stage Phase transition stage Temperature decrease in solid-state stage

Time / min

60

50

40

30 control 175W 224W 288W 360W 418W

Electrical power of ultrasound / W

Fig. 3. The time spent on each freezing stage under ultrasound at different power levels.. Mean values standard deviation of three replicated measurements.

heat transfer enhancement were much more than the effect of heat generation; the total freezing time was shorter than that of the conventional freezing. Especially, at 288 and 360 W power level, the total processing time signicantly decreased 11.2% and 13.7% (P < 0.05), respectively, compared to the conventional freezing. The acquired times for each stage of freezing process are shown in Fig. 3. The dependence of the freezing time on electric power is different for each stage because of the different degrees of ultrasonic effects in each stage. Regarding the time spent in the liquid-state temperature decrease stage, UAF did only a limited benet with a slightly shorter time at 288 and 360 W power levels resulting from the domination of heat transfer enhancement inside the dough. However, at 175, 224, and 418 W power levels, the freezing efciency was depressed due to the domination of heat generation. As known the heat generation was caused by ultrasonic absorption and scattering in high heterogeneous and high acoustic attenuated material like dough (McClements, 1997), and the more heterogeneous the material is (for example, the greater differences the properties between the uids and the solids inside the dough are), the greater heat would be generated (Lee et al., 2004). During this stage the ultrasonic wave propagated through unfrozen dough, resultant ultrasound-induced heat generation therein were considerable as a result of substantial difference in the properties between the uid and the solid-state. So ultrasound may improve the freezing rate of this stage limitedly. UAF have shortened the time spent in the phase transition stage at the 288 and 418 W power level with no signicant difference (P < 0.05), especially signicantly at 360 W power level (P < 0.05). During the phase transition stage, the ultrasonic cavitation bubble provided a favorable condition for the occurrence of heterogeneous primary nucleation of ice, and shock waves and micro-jets promoted secondary nucleation by breaking up the pre-existing dendritic ice crystals into tiny nuclei (Chow et al., 2003, 2004, 2005; Delgado et al., 2009; Delgado and Sun, 2011; Inada et al., 2001; Kiani et al., 2011, 2012; Petzold and Aguilera, 2009; Saclier et al., 2010; Zhang et al., 2001, 2003; Zheng and Sun, 2006). In Fig. 4 at a 100 magnication, the SEM images of the frozen dough fracture faces that were obtained through conventional freezing and the UAF at 360 W power level were compared and it can be easily noticed that after freeze-storage for one week under the same conditions, the angular pores of the frozen dough with ultrasound were smaller and denser. In addition, the roughness of the fracture face was reduced. The results indicate that ultrasound, under the appropriate conditions, can promote the formation of a large quan-

Fig. 4. SEM photographs of the fracture surface of the thin-diameter freezing dough rods that had been frozen and stored for one week after being frozen (a) with and (b) without ultrasound at 360 W power level. At a 100 magnication, the bar corresponds to 100 lm. GV represents gas voids, and AV represents angular voids.

300

100 Max breaking force Max breaking distance

250 80 200 60 150

100 Control 224W 288W 360W 418W

40

Electric power of ultrasound

Fig. 5. The maximum penetration forces and distances of frozen dough wafer processed UAF at different power levels measured by FTA. Mean values standard deviation of three replicated measurements.

Maximum penetration distance /mm

Maximum penetration force /g

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Table 1 Results of gas chromatography- mass spectroscopy analysis for the frozen doughs. No. Retention time (min) Compounds Molecular formula Relative content (%) Control 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 1.71 2.88 3.57 4.62 5.67 6.66 7.36 9.63 10.62 12.75 13.2 13.39 13.48 13.57 13.65 13.86 14.29 15.02 15.32 15.58 15.96 16.21 17.46 17.61 17.85 19.81 19.92 20.06 20.35 20.49 20.73 21.11 21.66 22.08 22.24 22.5 22.58 22.65 23.02 23.37 23.5 23.82 24.42 24.53 25.15 25.31 25.47 25.61 25.76 26 26.47 26.52 26.72 27.42 27.69 28.06 28.22 28.61 28.75 28.89 29.25 29.87 30.2 30.24 30.85 31.94 32.36 Acetone Isovaleraldehyde Valeraldehyde
DL-3-aminobutyric

UAF 0.51 0.02 0.99 0.12 0.99 70.47 N.D. N.D. 0.55 6.89 0.69 0.23 1.03 0.45 0.06 0.05 0.46 0.26 0.72 0.71 0.32 6.48 2.55 1.02 0.28 0.03 0.05 0.01 0.06 0.01 0.04 0.06 0.36 0.02 0.03 0.02 0.27 N.D. N.D. 0.02 0.03 0.04 0.01 0.09 0.07 0.07 N.D. 0.01 0.02 0.03 0.03 0.02 0.03 0.03 N.D. 0.01 0.09 0.02 0.17 0.08 0.05 0.02 0.05 N.D. 0.29 0.27 N.D.

acid 1-pentanol Caproaldehyde Trans-3-octen-2-ol Hexyl alcohol Heptaldehyde Cyclohexenecarbaldehyde Benzaldehyde 1-Octen-3-one 1-Octen-3-ol Trans,trans-2,4-nonadienal Vinyl hexanoate Isobutyl butyrate Octanal 2,4-Heptadienal 5-ethylcyclopentene-1-carbaldehyde 3-Octen-2-one 2-Heptyl-1,3-dioxalane octanalglycol acetal (E)-2-octenal 2-Hrptne-3-ol,4,5-dimethyl1-Nonanal Trans-2-hexenyl butyrate Oleyl alcohol 2-Nonenal 12,15-Octadecadiynoic acid methyl ester Ethyl benzoate 2,6,8-Trimethyldecane Ethyl caprylate Decanal Phenylazoresorcinol 3,7,11-Trimethyl-1-dodecanol Phenylacetic acid ethyl ester Dodecamethylcyclohexasiloxane 3-Heptylacrolein Acetic acid,triuoro-,1-methyluN.D.ecyl ester 4-Ethyl-2-methoxyphenol (E,E)-2,4-Dodecadiena N,N-Dibutylformamide Trans,trans-2,4-decadienal 5-isopropenyl-beta,2-dimethylcyclopent-1-ene-1-propyl acetate 9-Hexadecenoic acid 2-Butanone, 4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-, (R)()-Alpha-Cedrene Cedrene 2-Bromooctadecanal Nerolidyl acetate 2,6-Di-tert-butyl-p-benzoquinone Cocal 2,6-Di-tert-butyl-4-methylphenol 2,4-Di-tert-butylphenol 3-terz-butyl-1,2-dihydronaphthalene Anthracene, 1,2,3,4,5,6-hexahydro2,5-dimethyluN.D.ecane Cedrol 2,20 ,5,50 -Tetramethylbiphenyl 1,7-Dicyclopentyl-4-n-octylheptane 3,30 ,5,50 -Tetramethylbiphenyl 3,40 -Diethyl-1,10 -biphenyl 9-Hexylheptadecane Phosphoric acid tris(2-chloro-1-methylethyl) ester 2-Ethylhexyl salicylate Phthalic acid-,isobutyl-,2-amyl ester Phthalic acid-,butyl-,2-amyl ester Hexadecanoic acid,1-(hydroxymethyl)-1,2-ethanediyl ester

C3H6O C5H10O C5H10O C4H9NO2 C5H12O C6H12O C8H16O C6H14O C7H14O C7H12O C7H6O C8H14O C8H16O C9H14O C8H14O2 C8H16O2 C8H16O C7H10O C8H12O C8H14O C10H20O2 C8H14O C9H18O C9H18O C10H18O2 C18H36O C9H16O C19H30O2 C9H10O2 C13H28 C10H20O2 C10H20O C9H14O C15H32O C10H12O2 C12H36O6Si6 C10H18O C17H25F3O2 C9H12O2 C12H20O C9H19NO C10H16O C15H24O2 C16H30O2 C13H22O C15H24 C15H24 C18H35BrO C17H28O2 C14H20O2 C13H16O C15H24O C14H22O C14H18 C14H16 C13H28 C15H26O C16H18 C25H48 C16H18 C16H18 C23H48 C9H18Cl3O4P C15H22O3 C17H24O4 C17H24O4 C35H68O5

0.57 0.05 1.17 0.3 1.64 69.06 0.19 0.3 0.68 6.95 0.87 0.14 1.22 0.26 0.17 0.1 0.33 0.12 0.77 0.42 1.42 3.92 0.62 0.5 0.03 0.07 0.07 0.04 0.2 0.04 0.05 0.31 0.04 0.02 0.25 0.05 N.D. 0.05 0.01 0.12 0.07 0.19 0.01 0.02 0.11 0.12 0.02 0.01 0.01 0.05 0.16 0.16 0.15 0.15 0.09 0.05 0.17 0.06 0.5 0.19 0.14 0.02 0.04 0.02 0.3 0.29 0.02

N.D. stands for not detected.

tity of tiny ice crystals inside the frozen dough and enhance the heat transfer to shorten the time needed for phase transition stage. Under ultrasound irradiation, the solid-state temperature decrease stage required less time in all cases in comparison to con-

ventional immersion freezing. In addition the dependence of time on the ultrasonic power was similar to those of the other two stages; the minimum time that was required for this stage was approximately 40 min at 288, 360, or 418 W power level.

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The results can be explained as that during this stage, most of the moisture inside had frozen, the residual solution had a high viscosity with slightly difference acoustic characteristic from the solid state, so the ultrasonic absorption and scattering had been weakened, and less heat was generated by the ultrasound than during the liquid-state temperature decrease stage. Ultrasound can enhance heat transfer and nucleation during this stage, furthermore the heat generation decreased, so the time needed for this stage was shortened markedly. Whether or not cavitation was generated, as well as the magnitude of cavitation intensity, was dependent on the ultrasonic parameters and the solutions properties. During the ultrasoundassisted dough-freezing process, only ultrasound with sufcient intensity (power level was more than 224 W) is capable of inducing cavitation inside the dough to enhance heat transfer and ice crystallization; however, when the frozen dough was irradiated by high-power ultrasound (at 418 W power level), the ultrasonic effects increased with too much heat generated inside of the dough. As a result of balance, the improved effect on the freezing process at 418 W power level is inferior to that induced by ultrasound at 360 W power level (Figs. 2 and 3). Moreover, as previously mentioned, ultrasound may attenuate more slowly inside dough sample during the phase transition stage and the solid-state temperature decrease stage than during the liquid-state temperature decrease stage, as a result, the induced ultrasonic cavitation was stronger during the phase transition stage and the solid-state temperature decrease stage. Therefore, the required times for completion of the phase transition and solid-state temperature decrease stages were shortened signicantly by UAF at 360 W power level (P < 0.05). 3.3. The elasticity of frozen dough is improved with UAF The maximum penetration distance of the FTA probe reects the extensibility of the frozen dough, whereas the maximum penetration force reects its elasticity (Tian, 2006). Fig. 5 depicts the value of the maximum penetration force and distance of the frozen dough that had been frozen with ultrasound at different power levels. The maximum dough penetration distances that were obtained through UAF were both between 50 and 57 mm, and they showed no signicant differences with conventional freezing (P < 0.05), it indicates that UAF has the slight effect on the extensibility of the frozen dough. Compared with the conventional freezing technique, the maximum penetration force of the frozen dough processed with UAF at 288, 360, and 418 W power level increased signicantly more than 30% (P < 0.05), indicated that the frozen dough which had been treated with ultrasound maintained considerable elasticity. During dough freezing and freeze-storage, ice-crystal expansion could damage the gluten network structure resulting in the deteriorations of quality of frozen dough, such as post-thawing elasticity, extensibility, and air-holding capability. Ultrasound enhanced the heat transfer and ice crystal nucleation during UAF process, a large number of tiny ice crystals were formed inside the frozen dough. The ice crystals could not expand enough to damage the visco-elastic gluten network (Song et al., 2009), which is greatly responsible for the properties of dough, including dough elasticity (Shewry and Halford, 2001). UAF and subsequent freeze-storage caused less damage to the macromolecules, such as gluten and starch, in the frozen dough, resulting in an improved frozen dough quality. 3.4. GCMS analysis on frozen dough The GCMS analysis results on the doughs which were frozen with UAF at 360 W power level and without UAF (controlled dough) are shown in Table 1. There are 59 and 66 kinds of chemical

ingredients can be identied in the UAF dough and controlled dough, respectively. In these identied compounds there are 58 identical ingredients, which take the proportions of 95.54% and 98.09% relative concentrations in the UAF dough and controlled dough, respectively, and three dominant ingredients are the same as caproaldehyde, cyclohexenecarbaldehyde and (E)-2-octenal, which stand for 79.93% and 83.84% relative concentrations in the UAF dough and controlled dough, respectively. There are 8 kinds of detected ingredients (accounting for only 0.7% relative concentration) less in UAF dough than in controlled dough, and compared with UAF dough the only ingredient which is not detected in controlled dough is 3-Heptylacrolein (0.27% relative concentration in UAF dough), which is approved as food avor by Flavor and Extract Manufacturers Association of USA. The GCMS analysis results show that UAF processing has little inuences on the avor of the dough at 360 W power level. 4. Conclusion The effects of ultrasound irradiation on the dough-freezing process, as well as the quality and microstructure of ultrasound-assisted frozen dough, were investigated. Similar to conventional food-freezing processes, the UAF process could be divided into three stages named as liquid-state temperature decrease stage, phase transition stage, and solid-state temperature decrease stage. With the enhancement of convection heat-transfer and ice nucleation inside the dough by ultrasonic cavitation the total freezing times shortened signicantly more than 11% (P < 0.05) at 288 and 360 W power level. For the heat generation inside the dough, ultrasound improve the freezing-rate at the phase transition stage and the solid-state temperature decrease stage more efciently than that at the liquid-state temperature decrease stage, the results show that ultrasound should better be applied as soon as the temperature reach to the equilibrium freezing temperature. And the quality of the ultrasound-assisted frozen dough was improved, their elasticity increased signicantly at 288, 360, and 418 W ultrasonic power level (P < 0.05). Moreover, the results of GCMS analysis show that UAF processing has little inuences on the avor of dough. Although lacks of some additives (e.g., yeast and salt) in comparison with the standard contents of bread dough, the experimental dough can represent the complex food system for its high heterogeneity and high acoustic attenuated, the results provided useful information for the application of UAF in food processing in the near future. Acknowledgements The authors are grateful for nancial support from The National Natural Science Funds of China (Grant No. 31130042, 31171630), The Fundamental Research Funds for the Central Universities, SCUT (Grant No. 2012ZG0007, 2011ZM0095), The Program for New Century Excellent Talents in University (Grant No. NCET-10-0362), and The Major State Basic Research Development Program of China (973 Program) (Grant No. 2012CB720801). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.jfoodeng.2012.07. 033. References
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