JFS E: Food Engineering and Physical Properties

Effect of Sucrose on Physical Properties of Spray-Dried Whole Milk Powder

U.V. LAY MA, G.R. ZIEGLER, AND J.D. FLOROS
ABSTRACT: Spray-dried whole milk powders were prepared from whole condensed milk with various sucrose concentrations (0%, 2.5%, 5%, 7.5%, and 10% w/w), and their glass transition temperature and some physical properties of importance in chocolate manufacture were evaluated. In milk powder samples, the glass transition temperature and free-fat content decreased in a nonlinear manner with sucrose addition. Moreover, increasing sucrose concentration reduced the formation of dents on the particle surface. Addition of sucrose in whole condensed milk increased linearly the apparent particle density and in a nonlinear manner the particle size of spray-dried milk powders. The particle size volume distribution of milk powders with the highest sucrose concentration differed from the log-normal distribution of the other samples due to the formation of large agglomerates. Neither vacuole volume, nor the amorphous state of milk powders was affected by sucrose addition. Keywords: free fat, glass transition temperature, particle size, spray-dried whole milk powder, sucrose

Lactose crystallization is achieved when lactose is exposed to temperatures above its Tg (Roos and Karel 1990, 1992; Slade and Levine 1991). Roos (2002) reported that the Tg of dairy dried products is governed principally by the carbohydrate components. For example, the Tg of milk powder is almost the same as the Tg of pure lactose at the same water content (Jouppila and Roos 1994; Jouppila and others 1997; Roos 2002; Fern ndez and others 2003). Water acts a as a plasticizer and reduces the Tg of amorphous materials. Therefore, addition of water to milk powder reduces its Tg and crystallization of lactose can be achieved at lower temperature. Other factors can also affect the Tg of milk powders, including material composition and the use of other plasticizers (Roos and Karel 1990). Sucrose is one of the ingredients used in chocolate manufacture and has a Tg lower than that of lactose. The Tg of amorphous lactose was reported to be in the range of 97 to 105 C (Roos and Karel 1990, 1991; Arvanitoyannis and Blanshard 1994; Jouppila and Roos 1994; Fennema 1996; Jouppila and others 1997; Ottenhof and others 2003; Haque and Roos 2004a), while the Tg of amorphous sucrose was in a much lower range of 52 to 70 C (Roos and Karel 1990; Arvanitoyannis and Blanshard 1994; Fennema 1996; Ottenhof and others 2003). Arvanitoyannis and Blanshard (1994) reported that a mixture of lactose and sucrose has a Tg and crystallization temperature lower than those of pure lactose. However, crystallization of lactose/sucrose mixtures may be greatly affected by the systems components and processing conditions. For example, Vega and Roos (2007) could not detect crystallization in sucrose/lactose and sucrose/lactose/casein systems after equilibration under vapor pressures between 0% and 44%, while crystallization occurred when only one of the sugars was used. On the other hand, Arvanitoyannis and Blanshard (1994) detected crystallization of sugars in sucrose/lactose mixtures stored at various storage temperatures. Thus, it is possible that the incorporation of sucrose in SDWMP may decrease its Tg, allowing lactose and sucrose crystallization at a lower temperature without water addition, and consequently inMS 20080080 Submitted 2/1/2008, Accepted 8/17/2008. Authors are with creasing the free-fat content. Therefore, addition of sucrose to milk Dept. of Food Science, The Pennsylvania State Univ., 202 Food Science powder may be beneficial for the manufacture of milk chocolate. Building, University Park, PA 16802, U.S.A. Direct inquiries to author Floros Previous researchers have reported how physical properties and (E-mail: jdf10@psu.edu). microstructure of spray-dried dairy powders are affected by lactose

Introduction

n the manufacture of chocolate, cocoa butter is the most expensive component. For this reason, chocolate manufacturers desire a proper chocolate flow behavior with the minimum amount of this ingredient (Verhey 1986; Aguilar 1993). The amount of cocoa butter used can be reduced by using whole milk powder with high free-fat content (Verhey 1986). In addition to cost reduction, free fat from milk has antiblooming properties and results in chocolate with softer texture (Baker and others 2003; Liang and Hartel 2004). In chocolate manufacture, roller dried milk powder is preferred over spray-dried milk powder, principally because of its higher freefat level. However, roller drying is substantially more expensive than spray drying due to higher energy consumption (Hansen and Hansen 1990). Several methods to increase free-fat content in spray-dried whole milk powder (SDWMP) have been studied. Twomey and Keogh (1998) suggested that free-fat content may be increased by increasing nozzle pressure and decreasing nozzle size. Additionally, various authors have reported that crystallization of amorphous lactose in the milk powder particle can increase free-fat content (Saito 1985; Aguilar and Ziegler 1994b; Faldt and Bergenstahl 1996; Baker and others 2003). Lactose crystallization results in cracks on the surface of the particles releasing the encapsulated fat (King 1965). Koc and others (2003) induced lactose crystallization by exposing milk powder to high shear and elevated temperature. However, high temperature may produce caramelization and/or burnt flavors. Similarly, Baker and others (2003) described a process to increase the free fat of SDWMP by crystallizing the lactose present in milk powder. During this process, the milk powder is mixed with water, and lactose crystallization is induced by shearing and heating the mixture above its glass transition temperature (Tg). Unfortunately, addition of water negatively affects the rheological properties of chocolate.

C 2008 Institute of Food Technologists R doi: 10.1111/j.1750-3841.2008.00955.x

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concentration (Aguilar and Ziegler 1994a, 1994b) or physical state (amorphous or crystalline) of lactose or trehalose (Vega and others 2007). However, to our knowledge, there is no published research on how addition of various amounts of sucrose affects the Tg and other physical properties of SDWMP Our objective was to study the . effect of sucrose addition in the spray-dried whole milk on the milk powders Tg and other physical properties of interest in chocolate manufacture, such as particle size, total and free-fat content, density, and vacuole volume. The change in specific heat ( Cp) at the glass transition range was calculated, and Tg was reported as the temperature at half Cp.

Particle size
Particle size distribution of milk powder samples was measured using a MasterSizer R laser light scattering particle size analyzer (Malvern Instruments Ltd., Malvern, England, U.K.) (Aguilar 1993; Ziegler and Langiotti 2003). A 15-mL sample presentation unit and a 100-mm lens were used. Milk powder was dispersed at room temperature in isobutanol (Isobutanol, ACS, 99+%, Alfa Aesar R , Ward Hill, Mass., U.S.A.) at an obscuration value of approximately 0.25, corresponding to a volume concentration of approximately 0.07%. To ensure breakage of agglomerates, the dispersion was vigorously agitated with a vortexer at 1700 rpm for 1 min (Mini vortexer MV1, VWR Scientific Products, IKA R Works, Inc., Wilmington, N.C., U.S.A.) and stirred for 5 min using a magnetic stirrer. The dispersion was constantly stirred during the analysis to ensure that all particles were well dispersed. Particle size was reported as the mean diameter over the volume distribution (D [4,3] ).

Materials and Methods

Sample preparation
Whole condensed milk with 35% total solids supplied by Dietrichs Milk Products (Middleburry, Pa., U.S.A.) was used. Various amounts of sucrose were added in the whole condensed milk to obtain a nominal sucrose concentration of 0%, 2.5%, 5%, 7.5%, and 10% w/w. Milk samples were stirred for 30 min to ensure complete dissolution of sucrose as determined in preliminary experiments. Samples were stored at 4 C for no more than 24 h before spray drying.

E: Food Engineering & Physical Properties

Total milk fat content

Total fat content of milk powder samples was measured using a CEM Smart Trac System-5 and a CEM Smart Trac Rapid Fat Analyzer (CEM Corp., Matthews, N.C., U.S.A.). Approximately 1 g of milk powder was placed between 2 glass fiber sample pads, weighed, and dried in the Smart Trac System by microwave drying. Immediately after drying, samples were placed in the Smart Trac Rapid Fat Analyzer to determine total fat content by nuclear magnetic resonance. Total milk fat (F T ) content was reported as a percentage of milk powder (g/100 g milk powder).

Spray drying
Whole condensed milk was constantly stirred during the spray drying process to maintain homogeneity. Processing parameters were previously determined in a separate experiment (Lay Ma 2005). The milk was pumped at a flow rate of 60 mL/min controlled by a varistaltic pump (Simon Manostat R , Barnant Co., Barrington, Ill., U.S.A.) into a heat exchanger and was continuously preheated to 50 C. The milk was spray dried using a cocurrent portable spray dryer (Niro Atomizer, Hudson, Wis., U.S.A.) equipped with a 2-fluid pneumatic atomizer with external mixing. The air pressure was 68.9 kPa (10 psi), and the inlet and outlet air temperatures were 179 5 C and 72 4 C, respectively. After spray drying, milk powders were placed in a convection oven (Model 45EG, Precision-Jouan, Inc., Winchester, Va., U.S.A.) at 50 C for 24 h to standardize the water content of the samples. Following standardization and in order to prevent moisture absorption and lactose crystallization, samples were stored in 2 polyethylene bags (one inside the other) in a desiccator at room temperature for no more than 1 wk until use.

Free fat
Free-fat content of milk powder samples was determined by the method described by Koc and others (2003). Approximately 2 g of milk powder (w i ) were suspended in 15 mL of n-pentane (OnmiSolv R , High Purity Solvent, EMD Chemicals, Inc., Gibbstown, N.J., U.S.A.) in a stoppered flask. The suspension was stirred until all milk powder particles were well dispersed. Every 30 min, the suspension was manually stirred by shaking the flask for 15 s. After 2 h, the suspension was placed in tubes and centrifuged in a benchtop centrifuge for 10 min at 3500 rpm (AllegraTM 6, Beckman Coulter, Inc., Palo Alto, Calif., U.S.A.). Then, 2 mL of clear supernatant were placed in a preweighed aluminum dish and dried in a convection oven (Model 45EG, Precision-Jouan, Inc.) at 80 C for 2 h. Samples were cooled in a desiccator at room temperature for 30 min. The sample was weighed again (w f ), and free-fat content (F f ) as grams of free fat per 100 g of milk powder (g/100 g milk powder), and percentage of free fat (%F f ) as grams of free fat per 100 g of total fat (g/100 g total fat) were calculated (Aguilar and Ziegler 1994a) by the following 2 equations: F f = 100(7.5w f /wi ) %F f = 100F f /FT (1) (2)

Water content
Water content of milk powders was measured using a Karl Fischer titrator (Mettler Toledo DL31, Columbus, Ohio, U.S.A.), a 1-component reagent (Aquastar 1-comp5, Emd chemicals, Gibbstown, N.J., U.S.A.) as titrant, anhydrous methanol as solvent (J.T. Baker, Mallinckrodt Baker, Inc., Phillisburg, N.J., U.S.A), and water standard-10 as the Karl Fischer standard (Riedel-de Ha n, e Seelze, Germany). Approximately 40 mL of methanol were pumped in the titration vessel and pretitrated, and 1 g of milk powder was added to the solvent and titrated with the reagent. Water content was reported as a percentage of milk powder (%w/w).

Glass transition temperature

Tg of milk powder samples was determined using a differential scanning calorimeter (DSC-7, Perkin-Elmer Corp., Norwalk, Conn., U.S.A.). The instrument was calibrated using indium. An empty pan was used as a reference. Approximately 6 mg of sample were weighed (4D-4 autobalance, Perkin-Elmer Corp., Norwalk, Conn., U.S.A.) in a 20-L aluminum pan. The pan was hermetically sealed. The pan was held for 5 min at 20 C, heated to 130 C at a rate of 10 C/min, then immediately cooled to 20 C at a rate of 100 C/min, and finally reheated to 130 C at a rate of 10 C/min.
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where the number 7.5 in Eq. 1 is a correction factor: from the 15 mL of supernatant, only 2 mL were used to determine the amount of free fat.

True density, apparent density, and vacuole volume

True density of milk powders was measured using an air comparison pycnometer (Model 1305, Micromeritics, Norcross, Ga.,

Sucrose in spray-dried whole milk powder . . .

U.S.A.). Helium was used as the displacement gas. Approximately 1 g of milk powder was placed in a 5-mL measuring cup. Prior to density determination, air trapped within pores, cracks, or among particles was removed from the sample as described by the manufacturer (Micromeritics 1992). The sample chamber was pressurized to approximately 134.4 kPa (19.5 psi). After 5 min, the gas was expanded to a premeasured volume and the pressure was recorded. The drop of pressure on expansion was used to calculate sample volume. True density was then calculated by dividing the sample weight by its volume (Micromeritics 1992). Apparent density was measured and vacuole volume calculated following the procedures described by Daemen (1982) and Aguilar and Ziegler (1994a).

Results and Discussion

Water content and Tg
Water content of milk powders at the exit of the spray dryer was in the range of 3% to 5%. Because small amounts of water can greatly reduced the Tg of milk powders (Vuataz 2002), water content of samples was standardized after spray drying. As a result, no significant differences in water content (1.8% to 2%) were observed. A calculated composition of milk powders on a dry weight basis is shown in Table 1. Sucrose had a significant linear (P < 0.01) and quadratic effect (P < 0.10) on Tg (Table 2). As shown in Figure 1, Tg decreased with sucrose concentration. Previous studies (Roos 2002; Vega and others 2005) showed that Tg in dairy powders is driven by the carbohydrate components. The Tg of amorphous lactose was reported to be in the range of 97 to 105 C (Roos and Karel 1990, 1991; Arvanitoyannis and Blanshard 1994; Jouppila and Roos 1994; Fennema 1996; Jouppila and others 1997; Ottenhof and others 2003; Haque and Roos 2004a), while the Tg of amorphous sucrose was in a much lower range of 52 to 70 C (Roos and Karel 1990, 1991; Arvanitoyannis and Blanshard 1994; Fennema 1996; Ottenhof and others 2003). Therefore, it was expected that the Tg of milk powder would decrease with addition of sucrose. Our results were in agreement with a study by Arvanitoyannis and Blanshard (1994), where a mixture of sucrose and lactose had a Tg lower than that of pure lactose. A high variability of the measured Tg was observed (Figure 1). The mean Tg and standard deviation of the samples made from milk with 0%, 2.5%, 5%, 7.5%, and 10% sucrose were 76.9 1.7 C, 73.8 1.0 C, 69.4 2.2 C, 65.2 0.7 C, and 66.5 4.4 C, respectively. It was noticed that the standard deviation of the Tg values had a direct relationship with the variability of water content. The mean water content and standard deviation of the samples made from milk with 0%, 2.5%, 5%, 7.5%, and 10% sucrose were 1.94 0.08%, 1.89 0.07%, 1.93 0.17%, 2.07 0.02%, and 1.83 0.29%, respectively. Even though there were not statistically significant differences among mean water contents of samples, it appears that even a small variation in the amount of water can highly affect the Tg. Several researchers (Jouppila and Roos 1994; Jouppila and others 1997) used the GordonTaylor equation to predict the Tg of milk powders: Tg p = w1 Tg1 + kw2 Tg2 w1 + kw2 (4)

X-ray diffraction
The X-ray diffraction patterns of milk powders were obtained by an automated X-ray diffractometer (Rigaku Denki, Co. Ltd., Tokyo, Japan) to evaluate the crystalline and amorphous state of the samples. Milk powders after free-fat extraction were used. Samples were placed in an aluminum sample holder using heavy white mineral oil (Sigma Diagnostics, St. Louis, Mo., U.S.A.), and exposed to Cu K radiation ( = 0.15 nm). A current of 10 mA and a voltage of 30 kV were used. A pattern between 10 and 30 was obtained at a rate of 2 /min (Aguilar and Ziegler 1994a). Patterns showing characteristic crystalline peaks indicated that crystals were present, otherwise the sample was in the amorphous state (Koc and others 2003).

Scanning electron microscopy

Micrographs of milk powder samples were obtained using an environmental scanning electron microscope (Quanta 200 ESEM, FEI Co., Hillsboro, Ore., U.S.A.). Conductive carbon tape was placed on aluminum stubs and covered with a thin layer of milk powder. In the ESEM, samples were observed under a low vacuum mode of 0.10 kPa (0.75 Torr) and voltage of 20 kV.

Statistical analysis
Data were analyzed using MODDE statistical software (version 7.0.0.1, Umetrics, Ume , Sweden) and the RSREG procedure of SAS a for Windows (SAS 9.1, SAS Inst. Inc., Cary, N.C., U.S.A.). A 2nd-order polynomial was fitted to the data with sucrose concentration as the predictor variable:
2 Yi = 0 + 1 x1 + 11 x1 + i

(3)

where Y i are the responses, x 1 is sucrose concentration, i are the regression coefficients, and i the associated random error. Estimated regression parameters can be substituted in Eq. 3 to obtain an equation that can be used to predict the response of a dependent variable (that is, particle size, Tg, and so on).
Table 1 --- Composition of spray-dried milk powders.

where Tg p is the Tg of the product, Tg 1 and Tg 2 are the Tg of the components, w1 and w2 are their weight fraction, and k is a constant. Previous researchers (Jouppila and Roos 1994; Jouppila and others 1997) showed that the Tg of milk powder was almost equal to

% Dry weight % Sucrose in whole condensed milk 0 2.5 5 7.5 10

a Calculated b Calculated c

% Total solids in whole condensed milka 35.0 37.6 40.3 43.1 46.1

Sucrose 0.0 6.8 13.1 18.8 24.1

Lactoseb 36.9 34.1 31.8 29.5 27.6

Fatc 30.1 29.5 26.9 25.9 23.5

Proteinb 25.6 23.7 22.1 20.5 19.2

Other components (minerals, acids, and so on)b 8.1 7.5 7.0 6.5 6.1

based on the total solids information provided by the manufacturer. based on composition reported by Walstra and others (1999). Measured using a CEM Smart Trac System-5 and Rapid Fat Analyzer.

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Table 2 --- Estimated regression coefcients for the effect of sucrose added to whole condensed milk on the glass transition temperature (Tg), particle size, measured density, apparent density, total fat content, free fat, and percentage of free fat of spray-dried whole milk powders. All regression models were signicant at = 0.01. % free fat (g/100 g total fat)

that of lactose. Hence, Jouppila and others (1997) successfully predicted milk powders Tg with Eq. 4 using the Tg of water as Tg 2 , the weight fraction of water as w2 , Tg of lactose as Tg 1 , and the weight fraction of solids as w1 . Couchman and Karasz (1978) showed that in the GordonTaylor equation (Eq. 4) k = Cp 2 / Cp 1 , where Cp 1 and Cp 2 were the Cp at the glass transition of the components. Thus, these authors gave the following equation: Tg p = w1 Tg1 C p1 + w2 Tg2 C p2 w1 Tg1 + w2 Tg2 (5)

Free fat (g/100 g milk powder)

0.98 16.988 2.098a 0.068a ns

0.97 59.113 6.120a 0.145b ns

Total fat content (%w/w)

The CouchmanKarasz equation (Eq. 5) and the GordonTaylor equation (Eq. 4) can be used to calculate the Tg of a 2-component mixture (Roos 1995a; Gontard and Ring 1996; Bhandari and others 1997), but cannot be used for systems with more than 2 components. However, the CouchmanKarasz equation (Eq. 5) can be extended (Gontard and Ring 1996; Bhandari and others 1997) for mixtures with 3 components: Tg p = w1 Tg1 C p1 + w2 Tg2 C p2 + w3 Tg3 C p3 w1 Tg1 + w2 Tg2 + w3 Tg3 (6)

0.98 28.809 0.703a 0.005ns ns

Apparent density (g/mL)

0.56 0.987 0.001a 0.001ns ns

R2 Intercept ( 0 ) Linear ( 1 ) Quadratic ( 11 ) Lack of t ( = 0.05)

Regression coefcient ()

The letters a, b, and ns show the level of signicance: a = 1%, b = 10%, and ns = not signicant.

Measured density (g/mL)

Particle size (m)

0.76 77.203 2.080a 0.096b ns

Tg ( C)

0.86 41.417 0.895a 0.214b ns

0.62 1.130 0.025a 0.002a ns

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a,b,ns

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where w3 , Tg 3 , Cp 3 are the weight fraction, Tg, and Cp of the 3rd component in the system. In the present study, lactose and water were not the only components affecting the Tg of milk powders, but sucrose was also present. Thus, the Tg was calculated using Eq. 6 including sucrose as a 3rd component, and a calculated line was plotted (Figure 1). The following values were used for the calculations: Tg water = 135 C (Johari and others 1987); Tg lactose = 97 C (Jouppila and Roos 1994); Tg sucrose = 56.3 C (Arvanitoyannis and Blanshard 1994); Cp water = 1.94 J/g C (Sugisaki 1968); Cp lactose = 0.52 J/g C; and Cp sucrose = 0.76 J/g C (Arvanitoyannis and Blanshard 1994). As shown in Figure 1, Eq. 6 can roughly predict the Tg of the milk powder samples. This equation overestimates the Tg at 0% sucrose and underestimates the Tg at high sucrose content. The lack of predictive power of Eq. 6 can be attributed to the wide range of Tgs reported for amorphous lactose and sucrose. Tg values can vary depending on whether sealed or punctured pans were used during DSC analysis. For example, Jouppila and Roos (1994) reported a Tg of lactose of 97 C measured in sealed pans, while Haque and Roos (2004b) reported a Tg of anhydrous lactose of 105.4 C measured in punctured pans. These authors (Haque and Roos 2004b) suggested

Figure 1 --- Effect of sucrose added to whole condensed milk on the glass transition temperature of spray-dried whole milk powder with 2% water content.

Sucrose in spray-dried whole milk powder . . .

that the higher Tg value was probably caused by the evaporation of As observed in the micrographs (Figure 4), large agglomerates residual water during Tg determination. In addition, Tgs can be re- were formed in milk powders made from concentrated milk with ported as onset, midpoint, or end values. Moreover, it is difficult to 7.5% and 10% sucrose. However, agglomerates in samples with obtain accurate experimental values for Cp (Roos 1995a). 10% sucrose were of much larger size with many being larger than 200 m (Figure 4f). These observations agree with particle size volParticle size ume distribution results (Figure 3) and can be explained by the Particle size of milk powder samples increased with higher su- stickiness of sucrose-rich products. Bhandari and others (1997) excrose concentration (Figure 2). Sucrose concentration had a signif- plained that when the temperature of spray-dried sugar-rich prodicant linear (P < 0.01) and quadratic (P < 0.10) effect on the particle ucts reaches 20 C above Tg, particles become sticky. According to Roos (1995b), particles of food powders may become sticky even at size of whole milk powders (Table 2). Previous studies reported that higher total solid content in con- temperatures of 10 C above their Tg. Milk powder samples made from condensed milk with 7.5% and centrated milk significantly increases mean particle size in spraydried milk powders (Buma 1971a; Baldwin and others 1980). Addi- 10% sucrose had an average Tg of about 65 C (Figure 1). However, tion of sucrose in the whole condensed milk increased its total solid Tgs were measured after some water was removed as described precontent, resulting in higher viscosity (Baldwin and others 1980; Al viously. It is well known that in amorphous materials, water acts as Asheh and others 2003), causing coarse atomization during spray a plasticizer and its removal increases the Tg of the product. Vuataz drying (Masters 1985), and consequently producing larger particle (2002) showed that decreasing water content of whole milk powder from 4% to 2% and from 3% to 2% increased its Tg by approximately size (Elversson and others 2003). Aguilar and Ziegler (1994a) showed that particle size of SDWMP 27 C and 14 C, respectively. Hence, the Tgs of milk powders at exhibits a log-normal volume distribution. In the present study, the exit of the spray dryer were much lower than those shown in samples prepared from condensed milk with sucrose concentra- Figure 1. Masters (1985) described that the temperature of dried tion up to 7.5% also seemed to have particle size with a log-normal particles at the end of the spray drying process is generally near the volume distribution (Figure 3). However, samples with 10% sucrose outlet air temperature. In the present study, the outlet air temperahad a different particle size distribution as shown in Figure 3, indi- ture was 72 4 C. Therefore, the product temperature at the end of the spray drying process might have been close to the sticky cating the presence of much larger particles (>100 m). temperature, resulting in plasticization of particle surface and particle agglomeration. It is important to point out, that as the outlet temperature approaches the sticky temperature, particles not only will agglomerate, but also will stick to the walls of the spray dryer, resulting in low product recovery (Bhandari and others 1997). This was observed in the present experiment and lower yield was obtained in samples made from milk with 7.5% and 10% sucrose concentration. Milk powder particles with 0% sucrose had dents on the surface (indicated with arrows in Figure 4). As sucrose concentration increased, the number of dents observed was reduced (Figure 4b) and eventually the dents disappeared at higher sucrose content (Figure 4c to 4f). Verhey (1972) described that during atomizaFigure 2 --- Effect of sucrose added to whole condensed tion, air dispersed in milk forms bubbles. Subsequently, during milk on the particle size of spray-dried whole milk drying, air can either expand (Verhey 1972) to form air vacuoles powder. in the particle or escape outside the particle leaving a void and resulting in collapse of the particle (Aguilar and Ziegler 1994a). Verhey (1972) also explained that for air vacuoles to be formed, a hard particle surface must be present. Droplets of condensed milk with low sucrose content had lower total solids content, which may have resulted in lower liquid viscosity and thus, faster diffusion of air from the interior to the surface of the droplet, leaving empty spaces in the particle. As a result, milk powder structure collapsed forming dents on the surface (Figure 4a and b). On the other hand, the diffusion of air in milk with high sucrose content was probably slower due to the higher total solids content. In addition, diffusion of water from the interior of the particle to the surface was slower than the rate of water evaporation from the surface to the air. As a result, particles with a hard surface were formed, increasing the probability of air entrapment and vacuole formation (Aguilar and Ziegler 1994a), and thus preventing the formation of dents (Figure 4d to 4f).

Density and vacuole volume

True density of SDWMPs has been reported in the range of Figure 3 --- Effect of sucrose added to whole condensed milk on the particle size volume distribution of spray- 1.28 to 1.30 g/mL (Buma 1965; Walstra and others 1999). Aguilar dried whole milk powder. and Ziegler (1994b) explained that true density is independent of
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air vacuole volume and is the density of the solid matrix. In the present study, the density of milk powder samples with 0% sucrose measured using the pycnometer was 1.14 g/mL, which is lower than the previously reported true density. The true density determined using the pycnometer is the density of the solid part of the sample, only if there were no closed pores (Micromeritics 1992) surrounding air vacuoles, so that helium could penetrate during density determination. Thus, it is possible that in the present study, milk powders had air vacuoles surrounded by a layer of solid matrix without pores or cracks, or with clogged pores. Therefore, during density determination, the air in some vacuoles could not be replaced by helium, and when measuring the sample volume, the volume of some air cells was also included. Consequently, the density measured using the pycnometer represented both the solid matrix and air trapped in the particle. Thus, the method used did not measure the true density. Previous studies reported that increasing lactose concentration (Aguilar and Ziegler 1994a, 1994b) or other nonfat solids (Walstra and others 1999) increases the true density of milk powders. Therefore, it was expected that addition of sucrose would increase the density of the milk particles. The expected results were in agreement for the samples made from milk with 0%, 2.5%, and 5% sucrose. However, above 5% sucrose concentration, the measured density did not increase (Figure 5). Daemen (1982) described that particle porosity can be prevented by using concentrated feed with high total solids content. The same author also explained that particles may be produced without open pores or cracks having completely enclosed air vacuoles. Addition of sucrose to the milk before spray drying increased the total solids content of the feed, thus, it is possible that milk powders with high sucrose concentration had more air vacuoles surrounded by a layer of solid matrix without pores or cracks. Hence, high sucrose content in spray-dried milk powders may delay diffusion or exchange of gasses or other materials between the interior of the particle and the surrounding. In addition to particle porosity, particle size and shape may have affected this diffusion. Milk particles with higher sucrose content had larger particles (Figure 2) without dents on the surface (Figure 4d to 4f), hence smaller surface area per mass, and therefore, slower diffusion of gasses between the interior of the particle and the surroundings. Apparent density increased with addition of sucrose (Figure 6). The linear effect was highly significant (P < 0.01). Addition of

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Figure 4 --- Scanning electron micrographs of milk powders made from concentrated milk with (A) 0%, (B) 2.5% (C) 5%, (D) 7.5%, and (E and F) 10% sucrose. White arrows show the formation of dents.

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sucrose, which has higher true density than milk components, increased the apparent particle density. These results were in agreement with previous studies (Aguilar and Ziegler 1994a), where addition of lactose with a density of 1.52 g/mL increased the apparent particle density. Vacuole volume is calculated based on the apparent and true densities. Because the density measured by the pycnometer did not represent the real true density of milk powders, a true density was calculated (Figure 5) using 1.28 g/mL as the true density of whole milk powder (Buma 1965) and 1.59 g/mL as the true density of sucrose (Singh and Heldman 1993). Contrary to our expectations and observations, vacuole volume was not significantly affected by sucrose concentration (data not shown). An increase in total solids might have resulted in higher viscosity, increasing the probability of air entrapment and vacuole formation (Aguilar and Ziegler 1994a). However, in our case, it is possible that the limited range of sucrose concentration along with the high variation of the data probably did not allow this effect to be statistically significant.

Total milk fat content, free fat, and percentage of free fat
Total milk fat content decreased linearly (P < 0.01) with sucrose addition (Table 2) because sucrose reduced the relative proportion of the other milk components. Similarly, increasing sucrose concentration reduced free fat and percentage of free fat (Table 2 and Figure 7). One of the reasons for the reduced amount of free fat was the lower amount of total fat present in powders with higher sucrose content. However, if this was the only reason, then percentage of free fat would have remained the same, which is contrary to our findings (Figure 7). In addition to milk powder composition, particle surface area also affects free-fat content. According to Buma (1971b), part of the free fat is found on the surface of particles as patches or an outer layer. As discussed previously, addition of sucrose produced particles with smaller surface area per unit weight (larger particles without dents). As a result, such powders would have lower levels of surface fat and hence less free fat (Keogh and Figure 5 --- Effect of sucrose added to whole condensed others 2003). These results are in agreement with those of Aguilar milk on the measured density of spray-dried whole milk and Ziegler (1994b). powder. Free fat also exists inside particles and can be extracted through pores, cracks, or spaces left empty by the removal of surface/capillary fat (Buma 1971b). Previously, we discussed the formation of a hard shell, the possibility of the presence of clogged pores, and the absence of pores and cracks surrounding air vacuoles in particles with high sucrose concentration. Similarly, it is possible that in high-sucrose milk powders, the presence of a hard shell and the absence of pores and cracks surrounding some fat

Figure 6 --- Effect of sucrose added to whole condensed milk on the apparent density of spray-dried whole milk powder.

Figure 7 --- Effect of sucrose concentration in whole con- Figure 8 --- X-ray diffraction patterns of milk powders densed milk on the percentage of free fat of spray-dried made from whole condensed milk with sucrose concentration of (A) 0% and (B) 10%. whole milk powder. Vol. 73, Nr. 9, 2008JOURNAL OF FOOD SCIENCE E437

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Sucrose in spray-dried whole milk powder . . .

globules decreased the proportion of the extractable fat. Furthermore, sucrose addition increased the amount of solid material surrounding the fat globules, which in turn resulted in lower levels of extractable fat.
Buma TJ. 1965. The true density of spray milk powders and of certain constituents. Neth Milk Dairy J 19:24965. Buma TJ. 1971a. Free fat in spray-dried whole milk. 3. Particle size. Its estimation, influence of processing parameters and its relation to free-fat content. Neth Milk Dairy J 25:5372. Buma TJ. 1971b. Free fat in spray-dried whole milk. 10. A final report with a physical model for free fat in spray-dried milk. Neth Milk Dairy J 25:15974. Couchman PR, Karasz FE. 1978. A classical thermodynamic discussion of the effect of composition on glass transition temperatures. Macromolecules 11:1179. Daemen ALH. 1982. The estimation of the mean particle density, the vacuole volume and the porosity of spray-dried porous powders. Neth Milk Dairy J 36:53 64. Elversson J, Millqvist-Fureby A, Alderborn G, Elofsson U. 2003. Droplet and particle size relationship and shell thickness of inhalable lactose particles during spray drying. J Pharm Sci 92(4):90010. Faldt P, Bergenstahl B. 1996. Changes in surface composition of spray-dried food powders due to lactose crystallization. Food Sci Technol-Lebensm-Wiss Technol 29(56):43846. Fennema OR. 1996. Water and ice. In: Fennema OR, editor. Food chemistry. 3rd ed. New York: Marcel Dekker, Inc. p 1794. Fern ndez E, Schebor C, Chirife J. 2003. Glass transition temperature of regular and a lactose hydrolyzed milk powders. Food Sci Technol-Lebensm-Wiss Technol 36:547 51. Gontard N, Ring S. 1996. Edible wheat gluten film: Influence of water content on glass transition temperature. J Agric Food Chem 44(11):34748. Hansen SD, Hansen PS. 1990. Spray dried whole milk powder for the manufacture of milk chocolate. Scand Dairy Inf 4(2):7982. Haque MK, Roos YH. 2004a. Water plasticization and crystallization of lactose in spray-dried lactose/protein mixtures. J Food Sci 69(1):FEP239. Haque MK, Roos YH. 2004b. Water sorption and plasticization behavior of spray-dried lactose/protein mixtures. J Food Sci 69(8):E38491. Johari GP, Hallbrucker A, Mayer E. 1987. The glass-liquid transition of hyperquenched water. Nature 330(6148):5523. Jouppila K, Roos YH. 1994. Glass transitions and crystallization in milk powders. J Dairy Sci 77(10):290715. Jouppila K, Kansikas J, Roos YH. 1997. Glass transition, water plasticization, and lactose crystallization in skim milk powder. J Dairy Sci 80(12):315260. Keogh MK, Murray CA, OKennedy BT. 2003. Effects of ultrafiltration of whole milk on some properties of spray-dried milk powders. Int Dairy J 13(12):9951002. King N. 1965. The physical structure of dried milk. Dairy Sci Abstr 27:91104. Koc AB, Heinemann PH, Ziegler GR. 2003. A process for increasing the free fat content of spray-dried whole milk powder. J Food Sci 68(1):2106. Lay Ma UV. 2005. Sucrose in spray dried whole milk powder and the refining and conching processes in chocolate manufacture: a glass transition approach. [M.S.]. University Park: The Pennsylvania State Univ. 149 p. Liang B, Hartel RW. 2004. Effects of milk powders in milk chocolate. J Dairy Sci 87:20 31. Masters K. 1985. Spray drying handbook. 4th ed. New York: Halsted Press. 696 p. Micromeritics. 1992. Multivolume pycnometer 1305operators manual. Norcross, Ga.: Micromeritics Instrument Corp. Ottenhof MA, MacNaughtan W, Farhat IA. 2003. FTIR study of state and phase transitions of low moisture sucrose and lactose. Carbohydr Res 338(21):2195202. Roos YH. 1995a. Characterization of food polymers using state diagrams. J Food Eng 24(3):33960. Roos YH. 1995b. Glass transition-related physicochemical changes in foods. Food Technol 10:97102. Roos YH. 2002. Importance of glass transition and water activity to spray drying and stability of dairy powders. Lait 82(4):47584. Roos Y, Karel M. 1990. Differential scanning calorimetry study of phase transitions affecting the quality of dehydrated materials. Biotechnol Progr 6:15963. Roos Y, Karel M. 1991. Plasticizing effect of water on thermal behavior and crystallization of amorphous food models. J Food Sci 56(1):3843. Roos Y, Karel M. 1992. Crystallization of amorphous lactose. J Food Sci 57(3):7757. Saito Z. 1985. Particle structure in spray-dried whole milk and in instant skim milk powder as related to lactose crystallization. Food Microstruct 4(2):33340. Singh RK, Heldman DR. 1993. Introduction to food engineering. 2nd ed. San Diego, Calif.: Academic Press. 499 p. Slade L, Levine H. 1991. Beyond water activity: Recent advances based on an alternative approach to the assessment of food quality and safety. Crit Rev Food Sci Nutr 30:115360. Sugisaki M. 1968. Calorimetric study of the glassy state. IV. Heat capacities of glassy water and cubic ice. Bull Chem Soc Japan 41(11):25919. Twomey M, Keogh K. 1998. Milk powder in chocolate. Farm Food 8(1):911. Vega C, Roos YH. 2007. The state of aggregation of casein affects the storage stability of amorphous sucrose, lactose, and their mixtures. Food Biophys 2(1):109. Vega C, Douglas H, Roos Y. 2005. Spray drying of high-sucrose dairy emulsions: feasibility and physicochemical properties. J Food Sci 70(3):24451. Vega C, Douglas Goff H, Roos YH. 2007. Casein molecular assembly affects the properties of milk fat emulsions encapsulated in lactose or trehalose matrices. 17(6):683 95. Verhey JGP. 1972. Vacuole formation in spray powder particles 2. Location and prevention of air incorporation. Neth Milk Dairy J 26:20324. Verhey JGP. 1986. Physical-properties of dried milk in relation to chocolate manufacture. Neth Milk Dairy J 40(23):2618. Vuataz G. 2002. The phase diagram of milk: a new tool for optimising the drying process. Lait 82:485500. Walstra P, Geurts TJ, Noomen A, Jellema A, Van Boekel MAJS. 1999. Dairy technology. New York: Marcel Dekker, Inc. 727 p. Ziegler GR, Langiotti JP. 2003. 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X-ray diffraction patterns

All milk powder samples had a similar X-ray diffraction pattern (Figure 8). The absence of characteristic crystalline peaks in the patterns indicated that lactose and sucrose were in an amorphous state. The absence of crystals was confirmed by micrographs (Figure 4). The amorphous state of spray-dried particles is due to the rapid removal of water during spray drying (Bhandari and others 1997; Roos 2002). The fast removal of moisture causes a rapid increase in the viscosity of the droplet and the particle surface approaches the glassy state (Roos 2002).

E: Food Engineering & Physical Properties

Conclusions

ncorporation of sucrose in SDWMP significantly affected the physical properties of the product. The main changes observed due to sucrose addition were: decrease in Tg, total fat and free-fat content, increase in particle size and apparent density, and the formation of agglomerates without dents on the surface of the particles. A lower free-fat content and the absence of dents in SDWMP with higher lactose content have also been previously reported (Aguilar and Ziegler 1994a). We also found that it is possible that sucrose addition may affect the mass transfer properties of milk powders, resulting in slower exchange of substances between the interior and exterior of particles. The observed effects of sucrose addition to whole condensed milk on physical properties of SDWMP seem to be caused by the increased total solid content and the lower Tg. However, further research is necessary to study whether interaction of sucrose with milk proteins or other milk components can also affect these properties. The lower Tg of the high-sucrose milk powders may facilitate the release of the encapsulated milk fat during chocolate processing at a lower temperature than that of standard milk powder, which can be beneficial in chocolate manufacture.

Acknowledgments
This work was funded through The Pennsylvania Agricultural Experiment Station administered by The College of Agricultural Sciences of The Pennsylvania State Univ. The authors are grateful to Mr. Robert Lukas from The Classic Caramel Co. for donation of the whole condensed milk. The assistance of Mr. Konstantinos Matsos throughout this study is also gratefully acknowledged.

References
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