Study of the influence of soy lecithin addition on the wettability of buffalo
milk powder obtained by spray-drying

Martim Victor Hammes, Alexandre Hahn Englert, Caciano Pelayo Zap-

ata Noreña, Nilo Sérgio Medeiros Cardozo

PII: S0032-5910(15)00168-0
DOI: doi: 10.1016/j.powtec.2015.02.047
Reference: PTEC 10845

To appear in: Powder Technology

Received date: 18 November 2014

Revised date: 19 February 2015
Accepted date: 22 February 2015

Please cite this article as: Martim Victor Hammes, Alexandre Hahn Englert, Caciano
Pelayo Zapata Noreña, Nilo Sérgio Medeiros Cardozo, Study of the influence of soy
lecithin addition on the wettability of buffalo milk powder obtained by spray-drying,
Powder Technology (2015), doi: 10.1016/j.powtec.2015.02.047

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 ACCEPTED MANUSCRIPT

STUDY OF THE INFLUENCE OF SOY LECITHIN ADDITION ON THE WETTABILITY OF

BUFFALO MILK POWDER OBTAINED BY SPRAY-DRYING

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Martim Victor Hammes1, Alexandre Hahn Englert2, Caciano Pelayo Zapata Noreña3, Nilo Sérgio

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Medeiros Cardozo1*

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1
Laboratory of Polymer Technology and Processing, Department of Chemical Engineering, Federal University of Rio Grande

do Sul (UFRGS), Rua Eng. Luiz Englert, s/n., CEP 90040-040, Porto Alegre, RS, Brazil.
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Department of Physical Chemistry, Institute of Chemistry, Federal University of Rio Grande do Sul (UFRGS), Av. Bento
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Gonçalves, 9500, CEP 91501-970, Porto Alegre, RS, Brazil.

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Laboratory of Food Dehydration, Institute of Food Science and Technology (ICTA), Federal University of Rio Grande do Sul
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(UFRGS), Av. Bento Gonçalves, 9500, CEP 91501-970, Porto Alegre, RS, Brazil.
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e-mail: martim@enq.ufrgs.br, alexandre.englert@ufrgs.br, czapatan@ufrgs.br, nilo@enq.ufrgs.br.

* corresponding author: nilo@enq.ufrgs.br, phone: 55 51 3308 4075, fax: 55 51 3308 3277

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Abstract

In this study, buffalo milk powder was produced with and without added soy lecithin. The fresh

buffalo milk was partially skimmed, pasteurized, concentrated to 40% (mass percentage) of total solids

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and dried by spray-drying. For the samples prepared with lecithin, its addition was made prior to the

drying process in concentrations of 0.3, 0.5 and 1.0 g of lecithin/100 g of total solids in the concentrated

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milk. The effect of lecithin concentration on the moisture content, morphology, color, surface area,

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particle size distribution and wettability of the powdered milk produced was evaluated. The wettability

was assessed by the static wetting test and the Washburn technique, the latter giving the water contact

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angle (θ) of the powder material. The addition of lecithin decreased the wetting time (ranging from 5 min
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to 63.9 s) and θ (ranging from 89º to 81º, approximately) of the buffalo milk powder, but it did not show

much influence on the moisture, morphology, color, surface area and size distribution of the powder
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particles.
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Keywords: Buffalo milk powder, soy lecithin, Washburn technique, static wetting test, contact angle.
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1. Introduction

According to data from Faostat [1], the buffalo herd in 2011 yielded a milk production of about

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95.8 million tons (around 13% of the worldwide milk production). This number is only inferior to the

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bovine milk production (approximately 83.5%, with 614.6 million tons). However, in hot and humid

regions of the world, buffalos contribute in a more significant way than cows to the total milk production

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because of their ability to thrive in more severe conditions, being more resistant to disease [2]. Another

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favorable aspect of buffalo milk, in comparison to bovine milk, is related to its peculiar characteristics in

terms of composition, presenting higher contents of essential fatty acids, ascorbic acid, and mineral
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species, such as calcium and phosphorus [3–6]. The buffalo milk also provides more energy per unit

volume than the bovine milk, due to its higher content of fat and proteins, being therefore more economic
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for producers, processers and consumers [2,5].

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Another important aspect regarding buffalo milk was found in the study by Sheehan and

Phipatanakul [7], where the authors concluded that people allergic to bovine milk may not be allergic to
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buffalo milk. The authors have attributed this fact to the existence of allergenic proteins in bovine milk
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that are not present in buffalo milk.

The transformation of milk into a powder end product by means of a drying process is widely used

in the dairy industry. Powdered milk can be conserved for a much longer period of time and its

production reduces the cost of certain operations, such as packing, storing and transportation [8,9]. The

powdering process allows almost complete preservation of nutrients to be achieved [10–13]. In the case

of buffalo milk, powdering is particularly interesting for the industrialization of the product, as a way to

overcome problems related to production seasonality and the commercialization in low production

regions. This is because it makes it possible to store milk in the form of powder at periods of high

production, so that afterwards the demand can be fulfilled in periods where there is a lack of milk in the

market.
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The drying step determines the quality of the final powder, and the choice of the specific type of

dehydrator is dictated by the nature of the material to be dried, the desired product morphology, economic

factors and conditions of operation [14,15]. Spray-drying is the most commonly utilized method in the

industrial production of milk powder, because it generates a product of good quality with better sensorial

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and nutritional aspects than drum-drying, also being faster and cheaper than freeze-drying [12,16–20].

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A factor of great importance for dried food is its reconstitution time (when necessary), which will

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determine if the food can be considered an instant product [21]. The denomination of instant food is given

to products that are specially dehydrated in order to be easily reconstituted to liquid form [22,23]. The

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reconstitution consists in the rehydration of the powdered food with the same amount of water contained
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in the original product [22,24,25]. The reconstitution time of an instant food powder depends upon the

rates of four processes: wetting, sinking, dispersion and dissolution (if soluble) [26]; however, the rate
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limiting step is usually wetting [23], which is itself influenced by the wettability of the powder surface.
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The wetting of a solid surface by a liquid is generally evaluated through the contact angle [26–28].
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For food materials, their surface composition plays an important role in the wetting process, it being

reasonable to assume that, in general, hydrophobic components (e.g. lipids) at the surface produce high
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water contact angles, while a surface containing hydrophilic species (e.g. carbohydrates) generates low
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contact angles with water [26,29]. For example, in the case of milk powder, the preferential migration of

one of the milk components towards the powder surface during (and after) spray-drying can dramatically

alter its water contact angle (i.e. water wetting properties) [29].

The most widely known and utilized methods to assess the wettability of food powders are the

sessile drop technique, the Washburn technique and the static wetting test [30,31]. The sessile drop

technique can be used if the powder is homogeneous and for small particles (smaller than 500 μm), and

provides the apparent contact angle measurement by the direct analysis of drop shape; however, this

technique requires more expensive equipment [27,31]. The Washburn (or capillary rise) technique

consists essentially in monitoring the rise of a liquid through the empty spaces (i.e. pores) of a particle

bed due to capillary action. By measuring the liquid penetration rate through the porous bed for two
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distinct liquids: perfectly wetting and wetting (for which one wants to measure the contact angle), the

contact angle can be obtained [32–34]. The static wetting test consists in measuring the time necessary to

achieve complete wetting of a specific amount of powder when spread upon a quiescent water surface at a

specified temperature [16,29,30].

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The reconstitution capacity, for some products, can be obtained in the drying operation itself

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through a rigorous control of the process parameters, or by means of an additional agglomeration process

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[35]. In the agglomeration process, the spray-dried powder particles are humidified, swelling quickly and

closing the capillaries, so that their surfaces become sticky and they will adhere to each other to form

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agglomerates/conglomerates [29,36,37]. In large industries, it is the steps of agglomeration and

lecithination that give the powdered milk its instant character, via a fluidized bed unit added at the end of
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the spray-drying line [11,12,22]. Lecithin molecules have amphiphilic properties that enable them to be

aligned on the fat/water interface, with the hydrophilic moiety in the aqueous phase and the lipophilic
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moiety in the fat phase. The end result is a coating around the surface of the powder milk particles
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(containing fat) increasing their affinity for water [38].

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As an alternative route, Fonseca et al. [39] suggested, for the production of goat milk powder,
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direct lecithination in the concentrated milk, before the drying operation. In this way, it was possible to

eliminate the agglomeration step, with a significant decrease in capital and operational costs for a
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powdered milk production plant. Although until the present date, as far as we know, there is no work

using the direct addition of lecithin to concentrated buffalo milk, this route could be an alternative to the

production of buffalo milk powder on a small scale, and so make possible the commercialization of

buffalo milk in regions where this product is not yet on the market.

In this context, the general goal of the present study was to evaluate the wetting characteristics of

buffalo milk powder, obtained with different levels of soy lecithin added to the concentrated milk before

spray-drying. The effect of lecithin concentration on the moisture content, water activity, color,

morphology, particle size distribution and surface area of the powdered milk produced was also
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evaluated. The wettability was assessed by two techniques, the static wetting test and the Washburn

technique.

2. Materials and Methods

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2.1 Production of buffalo milk powder

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About 20 L of Mediterranean buffalo milk were collected in situ, pasteurized (63 ± 2 °C for 30 min

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in a jacketed vessel) and partially skimmed to approximately 1% fat (Casa das Desnatadeiras, model 154

GR, Brazil) in a rural property located in Gravataí (RS, Brazil). Subsequently, the milk was concentrated

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in a rotary vacuum evaporator (Fisatom, model 558, Brazil) at a temperature of 50 ± 3 °C under a vacuum
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of 720 mmHg, until a concentration of 40% (mass) of total solids was reached. The time lapse between

pasteurization and concentration was four days. The total content of solids in the concentrated milk was

measured according to the method 925.23A of the Association of Official Analytical Chemists [40].
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For the case of the milk samples in which soy lecithin was used (Lécet 150M, Caramuru Alimentos
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S.A, Intubiara, GO, Brazil), this substance was added to the concentrated milk after the evaporation
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process, in concentrations of 0.3, 0.5 and 1.0g of lecithin/100g of total solids in the milk. The dispersion

of the soy lecithin in the concentrated milk was done with the aid of an Ultra Turax (IKA, model T18B) at
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7,000 rpm for one minute. To avoid influence of the homogenization step on the final dispersion of

components, the same procedure was used for the samples without added lecithin. Subsequently, the

spray-drying process was conducted in a Mini-Spray-Dryer (LM MSDi 1.0, LABMAQ, Brazil) with a

feed nozzle orifice of 1mm diameter. The feeding of the dryer was done by a peristaltic pump at 0.60 L/h.

The inlet and outlet temperatures of the drying air stream were 140.5 ± 1 °C and 92 ± 2 °C, respectively.

The pressure of compressed air was 343 kPa and the atomization air flow rate was 40.5 L/h [39]. The

drying process, in each condition, was conducted in duplicate.

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2.2 Powdered milk characterization

The contents of fat, protein, moisture and ash were determined, respectively, by the methods

932.06, 930.29,927.05 and 930.30 from the Association of Official Analytical Chemists [40], and the

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lactose content was theoretically calculated by difference.

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The color of the surface of the milk powder particles was measured with a colorimeter (Colorium 2,

Delta Color, Brazil), previously calibrated. From the reflectance spectrum of the sample, the colorimetric

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parameters L, a, and b from the CIELAB scale were obtained as determined by the Commission

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International de l’Eclairage (CIE, 1976). The parameter L indicates clarity intensity (0 totally black and

100 totally white); the parameter a indicates green/red (green -a and red +a) and the parameter b indicates
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blue/yellow (-b blue and +b yellow). The milk powder samples were prepared for such measurements in a

Petri dish (7 cm internal diameter), where 10g were spread making a non-transparent layer.
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The water activity (aw) was measured in triplicate for the powder samples without lecithin and with
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1% lecithin, by means of a water activity laboratory instrument (Lab Master-aw, Novasina).

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The particle size distribution was determined for the four samples studied, using a laser diffraction

analyzer (CILAS 1180, Compagnie Industrielle des Lasers, France). Isopropyl alcohol was used as a
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liquid medium to disperse the particles [41], in order to avoid their dissolution during the measurements.

The measurement conducted with pure isopropyl alcohol was used as background (blank).

The surface area of the milk powders, produced with different lecithin concentrations, was obtained

by analysis of N2 adsorption data (Nova Station A, Quantachrome Instruments), using the multi-point

BET method [42].

The morphology of the milk powder particles was analyzed by scanning electron microscopy

(SEM). The samples were prepared by deposition of the solid particles onto aluminum sample holders

covered with double-sided carbon tapes, subsequently covered with a gold layer and analyzed in a JEOL

microscope (model JSM 6060), operating in 20kV.

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2.3 Wettability assessment of the powdered milk

The wettability of the powder was assessed by the static wetting test [16] and by the Washburn

technique [32,33].

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The static wetting test consisted, initially, in weighing a defined amount of powder (1g) and putting

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it on a glass slide (Figure 1a), located 1 cm above the liquid surface (distilled water), covering a cubic

container (cross-section area = 25 cm2). The glass slide was then quickly removed, causing the powder to

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fall over the surface of the water contained in the recipient (Figure 1b). The wetting time, i.e., the time

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necessary for the whole amount of powder to be wetted by the liquid, was measured. The temperature of

the water was 25 ± 3 °C. The analysis was conducted in triplicate for each sample of buffalo milk powder.
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The Washburn technique measurements were performed in a glass tube of 4 mm of internal

diameter containing a bed packed with powder particles (Figure 2). The bottom of the tube was closed
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with a small piece of filter paper (Unifil, average size of pores equal to 26 μm) to hold the particles inside
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the tube. Since the capillary rise of the liquid is influenced by the uniformity of the particle bed [34], the

tube was gently tapped 40 times during the insertion of the particles in the tube, to guarantee the
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uniformity of the prepared bed. The height of the particle bed was about 5 cm. The liquid (water or
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hexane), contained in a Petri dish, was brought into contact with the bottom of the tube and, with the aid

of an analytical balance, the mass of liquid rising by capillarity was recorded as a function of time [32]

using a digital video camera.

The capillary rise of the wetting liquid in the pores between the particles of the solid is described by

Equation 1 [32].

Eq. (1)

where is the penetrating liquid mass, is the particle bed constant, the surface tension of the liquid,

the specific mass of the liquid, the viscosity of the liquid, θ the liquid-solid-gas contact angle and the
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penetration time. The constant was determined by using hexane as the perfectly wetting liquid, for

which the contact angle can be considered zero. Then the contact angle for water was determined from

the slope of the versus curve obtained using water as the test fluid. The rising liquid temperature

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was kept at 20 ± 2 °C during all experiments. The corresponding values of surface tension and viscosity

utilized in Equation 1 were, respectively, 72.68 mN/m and 0.9920 mPa.s for water, and 18.40 mN/m and

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0.324 mPa.s for hexane [43]. The analysis was conducted in triplicate (for each liquid) for each sample of

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buffalo milk powder obtained.

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2.4 Statistical analysis
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The statistical analysis of the experimental data obtained was done by analysis of variance

(ANOVA) and the Tukey test (p < 0.05), using the software STATISTICA® (version 12) [44]. The results
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reported in this work consist on average of at least two replicates (n = 2) of the treatments (i.e., drying
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with different levels of lecithin added). The data presented in the tables are expressed as mean value ±
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standard deviation.
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3. Results and discussion

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3.1 Characterization

The results for the composition of the buffalo milk powder produced without added lecithin are

shown in Table 1.The value of total lipids (4.34 ± 0.30%) classifies the buffalo milk powder produced as

partially-skimmed [45].

Table 1. Composition of the milk powder produced without lecithin*.

Property Value

Protein (%) 46.6 ± 0.08

Total lipids (%) 4.34 ± 0.30

Ash (%) 7.84 ± 0.15

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Lactose (%) 41.22 ± 0.08

*Measurements were done in triplicate (relative errors lower than 5%). % in dry basis (d.b.) = g / 100 g of dry material.

The colorimetric parameters L, a, and b did not vary significantly among samples, and the values

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obtained were 85.4 ± 0.5, -3.85 ± 0.02 and 4.19 ± 0.06, respectively. The milk powder produced, both

with and without lecithination, was visually white, suggesting that the buffalo milk did not undergo

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Maillard reaction to any significant extent in the drying conditions employed. This reaction is common

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when milk is subjected to high temperatures [46–48]. The final moisture content of the milk powder

produced did not vary significantly due to the presence of lecithin, and the mean value obtained was

0.87% (dry basis).

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The values obtained for the water activity of the sample produced without lecithin and that with 1%

lecithin were 0.1465 ± 0.002 and 0.133 ± 0.001, respectively. These values are suitable in terms of
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product stability, since they are below the critical aw value reported for milk powder, which is
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approximately 0.37 [49]. Water activity values higher than 0.37 may result in undesired structural
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changes and decomposition reactions during storage at room temperature [50,51].

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Figures 3 and 4 show, respectively, photomicrographs obtained by SEM and the particle size
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distributions obtained by laser diffraction of the milk powder samples produced without and with added

lecithin (1%).

From the photomicrographs in Figure 3, it is possible to observe that the buffalo milk powder

presented the typical morphology found in powdered cow milk produced by spray-drying [52], which

results from the collapse or wrinkling of spherical particles. The relatively smooth surface observed,

according to Chen et al. [53], may represent a lower redistribution of the components of the milk (i.e.,

lower migration of fat and protein to the droplet surface).

Figure 4 shows that the powders obtained display broad particle size distribution, which is likely

related to differences in surface tension among the atomized milk droplets, as a consequence of the

colloidal structure of the concentrated milk [41]. In Figure 4 it is also possible to observe that samples
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without any added lecithin showed a bimodal particle size distribution, with particle sizes ranging

between 0.1 μm and 80 μm. It is also possible to observe that the addition of lecithin caused alterations in

the size distribution in comparison with the lecithin-free samples, while the characteristics and intensities

of such alterations were independent of the amount of lecithin added. The alterations observed with the

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addition of lecithin were a decrease in the upper limit of the particle size distribution to approximately

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40 μm, a change in shape of the distribution, and a decrease in the mean particle diameter (Table 2), given

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by the volume-moment mean diameter D[4,3] [54]. The greater uniformity in particle size distribution

observed for the samples with lecithin may be a consequence of the surface-active character of this

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additive. Concerning the shape of the distribution, it was also essentially bimodal, but with changes in the

proportions of the two peaks and with the appearance of a shoulder in the peak corresponding to higher
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diameters.
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Table 2. Mean particle diameters obtained in the particle size analysis via laser diffraction.
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Lecithin addition (%) Mean diameter* (μm)

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0 13.84±1.05a
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0.3 9.43± 0.5b

0.5 8.79± 0.6b

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1 10.97± 0.95b

*Means followed by the same letter do not differ significantly among each other by the Tukey test.

The results from particle size analysis also show that 60% (in volume) of the particles are within the

range of diameters commonly produced by spray-drying, which varies from 10 to 250 μm [55]. However,

the significant content of fine particles (diameters smaller than 9.5 μm) constitutes an aspect to be

addressed in future studies, due to its negative effect on the wettability and dispersibility of the powdered

milk [56]. Further, according to Salman et al. [57], the wetting time of a powder decreases as the diameter

of the particles increases, while for the case of instant powdered cow milk (skimmed), the particle size for

optimum dispersibility is 200 μm [24,58].

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Table 3 shows the values of the surface area of the buffalo milk powder samples produced and the

corresponding Tukey test results. The difference between the surface area of the powder produced

without lecithin and the values obtained for the milk powder with lecithin (at different concentrations) is

statistically significant. However, as observed for the mean particle diameter results, the absolute value of

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this difference is rather small and may be not important for practical purposes. Additionally, comparison

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of the results of the Tukey tests reported in Tables 2 and 3 indicates that the reduction in particle diameter

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due to the addition of lecithin was not directly related to the surface area of the buffalo milk powder

(partially skimmed). The decrease in surface area of the powdered product with added lecithin was also

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found by Millqvist-Fureby and Smith (2007) in the spray-drying of skimmed cow milk.
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Table 3. Surface area of buffalo milk powder obtained with different levels of lecithin.

Lecithin concentration (%) BET surface area (m²/g)

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0 2.45 ± 0.15a
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0.3 1.76 ± 0.26b

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0.5 1.34 ± 0.38b

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1 1.91 ± 0.27b
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3.2 Wettability analysis

Figure 5 shows the wetting times obtained in the static wetting test for the four samples studied. A

decrease in the wetting time of the buffalo milk powder with the addition of lecithin is observed. The

smallest wetting time (63.9 s) was observed with the highest level of added lecithin (1.0 g of lecithin/100

g of total solids in the concentrated milk). Additionally, the decrease of wetting time with increasing

quantity of lecithin was non-linear, showing a smaller slope for concentrations above 0.5 g lecithin/100 g

of total solids in the concentrated milk, as can be seen in Figure 5. Similar results were obtained by

Fonseca et al. [39] in the lecithination of goat’s milk, with wetting times varying from 356 s, for milk

powder produced without lecithin, to 73 s, for milk with 0.8% of lecithin. It is also important to highlight

that the buffalo milk powder produced without lecithination showed a wetting time (approximately 5 min)
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that was significantly lower than the value reported by Kim et al. [29] for a commercial bovine milk

powder with similar content of fat (with wetting time above 10 min). However, it is not possible to

identify the specific causes of this difference, since no information about the particle size distribution of

the bovine milk powder used was provided by the authors, nor other relevant factors, such as the process

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parameters, the conditions of concentration, pasteurization, and homogenization, as well as protein

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integrity.

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Figure 6 shows, as an example, the raw data obtained by the Washburn technique for the sample

with 1% of lecithin, expressed in terms of water mass decrease in the Petri dishes as a function of time.

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Baselines 1 and 2 (dashed lines in Figure 6) represent the extrapolation of the data corresponding to the
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evaporation of liquid before and after the experiment (i.e., tube in contact with liquid). The water

evaporation rate during the tests was evaluated as the average of the slopes of these two baselines and
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subtracted from the raw data (data represented by the square symbols in Figure 6) to eliminate the
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contribution of the evaporation process to the loss of mass. By this procedure, the mass of water that rose
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in the particle bed was obtained and plotted against time, as can be seen in Figure 7.
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In Figure 7, it is possible to observe three regions of different slopes. The initial region of higher
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slope (t < t1) is related to the water absorption by the filter paper used to support the particle bed. Since

milk powder is a water-soluble material, the existence of the third region (t > t2) with lower slope can be

explained by a decrease of the capillary rise rate due to swelling of the particles and/or changes in the

liquid properties (surface tension, viscosity) during measurement. Therefore, to properly obtain the water

contact angle, only data of the second region (i.e., between t1 and t2) were considered. A similar

procedure was used by Kirdponpattara et al. [32] in the analysis of the contact angle for powders/porous

materials, including nylon and polystyrene. With the selected data points, m2 versus t curves were

obtained, as shown in Figure 8 for the sample with 1% lecithin.

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Measurements based on this procedure were then performed using hexane as test fluid and the water

contact angle (θ) was estimated according to Equation 1, considering hexane as the perfectly wetting

fluid.

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In order to validate the methodology adopted, the contact angle for dehydroxylated quartz particles

(white quartz sand, 297 µm > size > 210 µm, Sigma-Aldrich®) was also determined, with the

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dehydroxylation conducted according to Muster et al. [60]. The dehydroxylation of the silanol groups (Si-

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OH) from the quartz surface was done using a temperature of 800 °C for 6 hours. For the resulting

particulate material, the contact angle was measured using the Washburn technique by the same

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methodology used for buffalo milk powder. The value obtained for the water contact angle was
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80.75 ± 2.9 °. A statistically identical value was found by Muster et al. [60] as 75 ± 3 ° for

dehydroxylated silica spheres in the same conditions of temperature/time.

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Therefore, the procedure described above was conducted for all other milk powder samples. The
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resulting values of contact angle for the buffalo milk powder produced with different lecithin levels are
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shown in Table 4.
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Table 4. Water contact angle (θ) for buffalo milk powder obtained with different lecithin levels.
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Lecithin (%, dry basis)  (º)*

0 89.01 ± 0.48a

0.3 87.32 ± 1.01a

0.5 82.73 ± 2.76b

1 81.21 ± 2.23b

*Means followed by the same letter do not differ significantly among each other according

to the Tukey test (p < 0.05 and n = 2)

Table 4 shows the decrease of the contact angle estimated by the Washburn technique with the

increase in the amount of lecithin added, in agreement with the corresponding decrease of the wetting
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time found in the static wetting test. However, conversely to the results of the static wetting test, in which

all samples presented significantly different wetting times, the contact angle values in Table 4 were

divided into only two sets of statistically different values, according to the Tukey test. These results

indicate that the static wetting test is more sensitive to differences of wettability among samples of milk

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powder than the Washburn technique.

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4. Conclusions

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The results of this study indicate that the addition of lecithin to the concentrated milk before the

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drying process significantly improves the wettability of the product in relation to that of the buffalo milk

powder produced without lecithin. The addition of lecithin had a strong effect on the wetting time, which
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was reduced from approximately 5 min (without lecithin) to 63.9 s (with 1% of lecithin added). There was

also a decrease in the water contact angle (θ) for buffalo milk powder (from approximately 87–89º to 81–
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83º), estimated by the Washburn technique, with increase in the amount of lecithin added. However,
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lecithin addition did not have any effect on the morphology, color (L = 85.4 ± 0.5, a = -3.85 ± 0.02 and b
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= 4.19 ± 0.06) and moisture content (0.87%, dry basis) of the powder particles. The surface area (around
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2 m2/g) and size distribution of the particles were affected by the addition of lecithin, but due to their

small absolute values the changes observed in these two variables are not expected to be important for
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practical applications. The powder containing 0.5 g lecithin/100g total solids presented wetting properties

that are desirable for a partially-skimmed buffalo milk powder.

Acknowledgments

The authors are grateful for financial support from Coordenação de Aperfeiçoamento de Pessoal de

Nível Superior/Programa Nacional de Pós-Doutorado (CAPES/PNPD) and Conselho Nacional de

Desenvolvimento Científico e Tecnológico (CNPq), Brazil.

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References

PT
[1] Faostat, Top production - Buffalo milk, whole, fresh -2011, 2013.

RI
SC
[2] J.W. Fuquay, J.S. Sindhu, S. Arora, Encyclopedia of Dairy Sciences, second ed., Academic Press,

London, 2011.

[3]
NU
S. Ahmad, J.F. Grongnet, F. Gaucheron, Effects of acidification on physico-chemical
MA
characteristics of buffalo milk: A comparison with cow’s milk, Food Chemistry 106 (2008) 11–17.

[4] S. Kang, M. Wanapat, A. Cherdthong, Effects of energy level and Leucaena leucocephala leaf
D

meal as a protein source on rumen fermentation efficiency and digestibility in swamp buffalo,
E

Animal Feed Science and Technology 174 (2012) 131–139.

PT

[5] O. Ménard, S. Ahmad, C. Lopez, Buffalo vs. cow milk fat globules: Size distribution, zeta-
CE

potential, compositions in total fatty acids and in polar lipids from the milk fat globule membrane,
AC

Food Chemistry 120 (2010) 544–551.

[6] H.T.H. Nguyen, L. Ong, C. Lefèvre, S.E. Kentish, S.L. Gras, The microstructure and

physicochemical properties of probiotic buffalo yoghurt during fermentation and storage: a

comparison with bovine yoghurt, Food and Bioprocess Technology 7 (2013) 937–953.

[7] W.J. Sheehan, W. Phipatanakul, Tolerance to water buffalo milk in a child with cow milk allergy,

Annals of Allergy, Asthma & Immunology: Official Publication of the American College of

Allergy, Asthma, & Immunology 102 (2009) 349.

[8] Y. Kitamura, H. Itoh, H. Echizen, Experimental vacuum spray drying of probiotic foods, included

with lactic acid bacteria, Journal of Food Processing and Preservation 33 (2009) 714–726.
 ACCEPTED MANUSCRIPT 17

[9] F.C. Prado, J.L. Parada, C.R. Soccol, Trends in non-dairy probiotic beverages, Food Research

International 41 (2008) 111–123.

[10] E. Valduga, L.C Paviani, J.R.D. Finzer, Análise química do leite de búfala em comparação ao leite

PT
de vaca, Alimentos Nutritivos (2006) 398–400.

RI
[11] Y.H. Hui, Dairy Science and Technology Handbook, v. 1, Wiley-Vch, London, 1993.

SC
[12] S.T. Coulter, Evaporation of water from milk by spray drying 1,2, Journal of Dairy Science 38

(1955) 1180–1184.

NU
[13] C. Gaiani, M. Morand, C. Sanchez, E.A. Tehrany, M. Jacquot, P. Schuck, et al., How surface
MA
composition of high milk proteins powders is influenced by spray-drying temperature, Colloids and

Surfaces B: Biointerfaces 75 (2010) 377–384.

E D

[14] N. Jinapong, M. Suphantharika, P. Jamnong, Production of instant soymilk powders by

PT

ultrafiltration, spray drying and fluidized bed agglomeration, Journal of Food Engineering 84

(2008) 194–205.
CE

[15] A. Schieber, P. Esquivel, V.M. Jiménez, Functional properties of coffee and coffee by-products,
AC

Food Research International 46 (2012) 488–495.

[16] A.M. Ceballos, G.I. Giraldo, C.E. Orrego, Effect of freezing rate on quality parameters of freeze

dried soursop fruit pulp, Journal of Food Engineering 111 (2012) 360–365.

[17] E.T. Koroishi, E.A. Boss, W. Maciel, M. Regina, R. Maciel Filho, Process development and

optimization for freeze-drying of natural orange juice, Journal of Food Process Engineering 32

(2009) 425–441.

[18] S.M. Patel, T. Doen, M.J. Pikal, Determination of end point of primary drying in freeze-drying

process control, Journal of Pharmaceutical Science and Technology 11 (2010) 73–84.

 ACCEPTED MANUSCRIPT 18

[19] C. Ratti, Advances in Food Dehydration, Contemporary Food Engineering Series, 2008.

[20] R.S. Reddy, C.T. Ramachandra, S. Hiregoudar, U. Nidoni, J. Ram, M. Kammar, Influence of

processing conditions on functional and reconstitution properties of milk powder made from

PT
Osmanabadi goat milk by spray drying, Small Ruminant Research 119 (2014) 130-137.

RI
[21] T.A. Shittu, M.O. Lawal, Factors affecting instant properties of powdered cocoa beverages, Food

SC
Chemistry 100 (2007) 91–98.

[22] A. Sharma, A.H. Jana, R.S. Chavan, Functionality of milk powders and milk-based powders for

NU
end use applications - A review, Comprehensive Reviews in Food Science and Food Safety 11
MA
(2012) 518–528.

[23] H. Schubert, Instantization of powdered food products, International Chemical Engineering 33

D

(1993) 28–45.
E
PT

[24] E. Neff, H.A.L. Morris, Agglomeration of milk powder and its influence on reconstitution

properties, Journal of Dairy Science 51 (1968) 330–338.

CE

[25] P. Walstra, Dairy Technology: Principles of Milk Properties and Processes, CRC Press, 1999.
AC

[26] L. Forny, S. Palzer, A. Marabi, Wetting, disintegration and dissolution of agglomerated water

soluble powders, Powder Technology 206 (2011) 72–78.

[27] A. Depalo, A.C. Santomaso, Wetting dynamics and contact angles of powders studied through

capillary rise experiments, Colloids and Surfaces A: Physicochemical and Engineering Aspects

436 (2013) 371–379.

[28] G. Barnes, I. Gentle, Interfacial Science: An Introduction, second ed., Oxford University Press,

New York, 2011.

 ACCEPTED MANUSCRIPT 19

[29] E.H.-J. Kim, X.D. Chen, D. Pearce, Surface characterization of four industrial spray-dried dairy

powders in relation to chemical composition, structure and wetting property, Colloids and Surfaces

B: Biointerfaces 26 (2002) 197–212.

PT
[30] B. Freudig, S. Hogekamp, H. Schubert, Dispersion of powders in liquids in a stirred vessel,

Chemical Engineering and Processing: Process Intensification 38 (1999) 525–532.

RI
SC
[31] L. Susana, F. Campaci, A.C. Santomaso, Wettability of mineral and metallic powders:

Applicability and limitations of sessile drop method and Washburn’s technique, Powder

NU
Technology 226 (2012) 68–77.
MA
[32] S. Kirdponpattara, M. Phisalaphong, B.Z. Newby, Applicability of Washburn capillary rise for

determining contact angles of powders/porous materials, Journal of Colloid and Interface Science
D

397 (2013) 169–76.

E
PT

[33] E.W. Washburn, The dynamics of capillary flow, Physical Review 17 (1921) 273–283.

[34] T.V. Subrahmanyam, C.A. Prestidge, J. Ralston, Contact angle and surface analysis studies of
CE

sphalerite particles, Minerals Engineering 9 (1996) 727–741.

AC

[35] M. Jayasundera, B. Adhikari, A. Ghandi, Surface modification of spray dried food and emulsion

powders with surface-active proteins: A review, Journal of Food Engineering 93 (2009) 266–277.

[36] H. Schubert, Principles of agglomeration, International Chemical Engineering 21 (1981) 363–377.

[37] A. Barkouti, C. Turchiuli, J.A. Carcel, E. Dumoulin, Milk powder agglomerate growth and

properties in fluidized bed agglomeration, Dairy Science & Technology 93 (2013) 523–535.

[38] X. Lu, Q. Lu, Z. Wang, Laser induced periodic structure on lecithin-doped polyimide film surface

and its ability to align liquid crystal molecules, Polymer 44 (2003) 4501–4507.
 ACCEPTED MANUSCRIPT 20

[39] C.R. Fonseca, M.S.G. Bento, C.A.F. Oliveira, E.S.M. Quintero, A.L. Gabas, C.A.F. Oliveira,

Physical properties of goat milk powder with soy lecithin added before spray drying, International

Journal of Food Science and Technology 46 (2011) 608–611.

PT
[40] AOAC, Association of Official Analytical Chemists; Official methods of Analysis, Volume 15,

Washington, 1990.

RI
SC
[41] J.J. Nijdam, T.A.G. Langrish, The effect of surface composition on the functional properties of

milk powders, Journal of Food Engineering 77 (2006) 919–925.

[42]
NU
S. Brunauer, P.H. Emmett, E. Teller, Adsorption of gases in multimolecular layers, Journal of the
MA
American Chemical Society 60 (1938) 309–319.

[43] D.R. Lide, CRC Handbook of Chemistry and Physics, CRC Press, Boca Raton, FL., 2005.
E D

[44] StatSoft Inc., STATISTICA®, (2013).

PT

[45] FIL-IDF, Dried milk, dried whey, dried buttermilk and dried butter serum. Determination of fat
CE

content (Rose-Gottlieb reference method). Standard 9C., Brussels, 1987.

AC

[46] B. Hiller, P.C. Lorenzen, Functional properties of milk proteins as affected by Maillard reaction

induced oligomerisation, Food Research International 43 (2010) 1155–1166.

[47] B.J.F. Hudson, J.M. Ames, The Maillard Reaction, Biochemistry of Food Proteins (1992) 99–153.

[48] M.A.J.S. Van Boekel, Effect of heating on Maillard reactions in milk, Food Chemistry 62 (1998)

403–414.

[49] K. Jouppila, Y.H. Roos, Glass transitions and crystallization in milk powders, Journal of Dairy

Science 77 (1994) 2907–2915.

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[50] J. Hardy, J. Scher, S. Banon, Water activity and hydration of dairy powders, Le Lait 82 (2002)

441–452.

[51] B. Bhandari, T. Howes, Implication of glass transition for the drying and stability of dried foods,

PT
Journal of Food Engineering 40 (1999) 71–79.

RI
[52] J.M. Aguilera, D.W. Stanley, Microstructural Principles of Food Processing and Engineering,

SC
second ed., Media, Springer Science & Business, New York,1999.

[53] X.D. Chen, E.H.-J. Kim, D. Pearce, Surface composition of industrial spray-dried milk powders. 2.

NU
Effects of spray drying conditions on the surface composition, Journal of Food Engineering 94
MA
(2009) 169–181.

[54] T. Allen, Powder Sampling and Particle Size Determination, first ed., Elsevier Science, New York,
D

2003.
E
PT

[55] M.E.C. Thomas, S. Desobry-Banon, S. Desobry, Milk powders ageing: effect on physical and

functional properties, Critical Reviews in Food Science and Nutrition 44 (2004) 297–322.
CE

[56] J.-L. Ilari, L. Mekkaoui, Physical properties of constitutive size classes of spray-dried skim milk
AC

powder and their mixtures, Le Lait 85 (2005) 279–294.

[57] A.D. Salman, M. Hounslow, E. Dumoulin, Fluidized bed agglomeration of skim milk powder:

Analysis of sampling for the follow-up of agglomerate growth, Powder Technology 238 (2013)

161–168.

[58] A. Thompson, M. Boland, H. Singh, Milk Proteins: From Expression to Food, second ed.,

Academic Press, Elsevier Science, 2014.

[59] A. Millqvist-Fureby, P. Smith, In-situ lecithination of dairy powders in spray-drying for

confectionery applications, Food Hydrocolloids 21 (2007) 920–927.

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[60] T.H. Muster, C.A. Prestidge, R.A. Hayes, Water adsorption kinetics and contact angles of silica

particles, Colloids and Surfaces A: Physicochemical and Engineering Aspects 176 (2001) 253–266.

PT
RI
SC
NU
MA
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PT
CE
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Figure captions

Figure 1. Apparatus used in the static wetting test: (a) glass slide in the initial position, loaded with the

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powder sample; (b) glass slide removed and sample spread on the surface of the water.

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Figure 2. Experimental apparatus utilized for the Washburn technique.

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Figure 3. Photomicrographies obtained by SEM of the buffalo milk powder samples: (a) without lecithin;

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(b) 1% lecithin.
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Figure 4. Particle size distribution of buffalo milk powder obtained with different concentrations of

lecithin.
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Figure 5. Wetting time as a function of the amount of lecithin added.

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Figure 6. Water mass decrease in the Petri dish as a function of time for the sample with 1% of lecithin.
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Figure 7. Mass of liquid rising by capillarity into the particle bed as a function of time for the sample

with 1% of lecithin.
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Figure 8. Squared mass of liquid rising by capillarity into the particle bed as a function of time for the

sample with 1% of lecithin.

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Highlights

Buffalo milk powder, with and without soy lecithin, was obtained by spray-drying> Powder wettability

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was assessed by the static wetting test and Washburn technique> Lecithination decreased wetting time
and water contact angle of the milk powder> No influence of lecithin was found on other powder

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properties (e.g. moisture).

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