LWT 40 (2007) 15931600

Water sorption and glass transition properties of spray dried lactose

hydrolysed skim milk powder
Ashok K. Shrestha
a,
, Tony Howes
b
, Benu P. Adhikari
a,b
, Bhesh R. Bhandari
c
a
Centre for Nutrition and Food Sciences, The University of Queensland, Brisbane, QLD 4072, Australia
b
School of Engineering, The University of Queensland, Brisbane, QLD 4072, Australia
c
School of Land and Food Sciences, The University of Queensland, Brisbane, QLD 4072, Australia
Received 29 May 2006; received in revised form 6 November 2006; accepted 7 November 2006
Abstract
The moisture sorption behaviour and glass transition temperature of spray dried skim milk powder with hydrolysed lactose (SMPHL)
were determined. Spray drying of skim milk with hydrolysed lactose resulted in very low cyclone recovery of 25% and a large amount of
powder remained stuck inside the spray dryer. The equilibrium moisture content of SMPHL was lower than that of lactose for each
range of water activity when humidied for 21 days at 23 1C using saturated salt solutions. Unlike lactose, SMPHL did not lose water
when the water activity exceeded 0.432 and no crystallization was noticed at water activity X0.753. The sorption isotherm data for
SMPHL tted well with the BET and GAB models with monolayer moisture contents of 7.55 and 8.27 g/100 g, respectively. The glass
transition temperature of anhydrous SMPHL was 49 1C. The critical water activity and moisture content for SMPHL were 0.15 and
2.4 g/100 g dry solid, respectively. The low critical values indicated hydrolysis of lactose necessities maintenance of very low moisture of
powder for its long-term stability.
r 2006 Swiss Society of Food Science and Technology. Published by Elsevier Ltd. All rights reserved.
Keywords: Skim milk powder with hydrolysed lactose; Glass transition temperature; Lactose; Stability
1. Introduction
Spray drying is the most common method of dehydrat-
ing milk and milk products. It involves rapid removal of
moisture leading to the formation of amorphous lactose
which forms a continuous matrix in which proteins, fat
globules, and air cells disperse (Aguilar & Ziegler, 1994).
Amorphous lactose and other sugars (if present) in milk
powders can undergo a glassy-to-rubbery transition when
held at a temperature higher than their glass transition
temperature (T
g
). Amorphous sugar particles are highly
hygroscopic and will absorb water at higher humidity
resulting in plasticization that lowers the T
g
of the particles
signicantly. The molecular mobility increases when
viscosity decreases and this happens when the product
temperature is around or more than its glass transition
temperature. These phenomenon trigger a chain of events
leading to stickiness, caking and crystallization (Jouppila &
Roos, 1994b; Roos & Karel, 1992). Stickiness of dairy
powder results in poor product quality, lower yield during
drying, operation problems and difculties in handling and
storage.
The major ingredient in milk powder is lactose which
has a relatively high T
g
of 97116 1C (Haque & Roos,
2004a; Hill, Craig, & Feely, 1998; Jouppila & Roos, 1994a;
Roos & Karel, 1990). The presence of other components
such as moisture, protein(s), fat, mineral and lactic acid
can largely affect the physico-chemical behaviours includ-
ing water absorption, glass transition temperature and
crystallization of the milk powders (Berlin, Anderson, &
Pallansch, 1973; Jouppila & Roos, 1994a, 1994b; Levine &
Slade, 1986).
Due to lactose intolerance in a signicant number of
world populations, lactose reduction in milk and milk
products has become a useful strategy in enhancing the
consumption of dairy products. Although milk with
reduced or almost zero lactose content is available in the
ARTICLE IN PRESS
www.elsevier.com/locate/lwt
0023-6438/$30.00 r 2006 Swiss Society of Food Science and Technology. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.lwt.2006.11.003

Corresponding author. Tel.: +61 2 33469 642; fax: +61 7 3365 1177.
E-mail address: a.shrestha@uq.edu.au (A.K. Shrestha).
market, the availability of reduced or hydrolysed lactose
milk powders are not widespread.
The glass transition temperature of a carbohydrate is
inversely proportional to its molecular weight (Fox &
Flory, 1950; Levine & Slade, 1990; Roos, 1993). Hydrolysis
of lactose produces low molecular weight monosacchar-
ides, glucose and galactose. The T
g
values of glucose and
galactose are 31 and 32 1C, respectively (Roos, 1993; Roos
& Karel, 1991a). Previous studies have also reported much
lower T
g
in skim milk powder with hydrolysed lactose
(Fernandez, Schebor, & Chirife, 2003; Jouppila & Roos,
1994b). It is clear that if there is a slight increase in
moisture content, the T
g
of milk powders containing
hydrolysed lactose will go below room temperature and
these products are likely to be stickier than the correspond-
ing powders. This would certainly result in signicant
changes in the spray drying behaviour and storage
stability of milk powders containing hydrolysed lactose
(Roos, 1993). The sorption behaviour and glass transition
temperatures of milk powders with hydrolysed lactose
prepared by freeze drying have been studied by Jouppila
and Roos (1994b) and Fernandez et al. (2003). However,
no data exists for similar studies using spray-dried milk
powder with hydrolysed lactose.
The objectives of this study were to determine the spray
drying behaviour of skim milk with hydrolysed lactose and
measure the water sorption behaviour and glass transition
temperature of the resulting powders to predict critical
water content and storage conditions.
2. Materials and methods
2.1. Materials
Lactose free (hydrolysed) skim milk (brand name
Liddells), manufactured by Liddell Group Pvt. Ltd.
Boronica, Vic., Australia, was purchased from the local
supermarket and stored in a refrigerator until spray-dried.
The composition of the milk as labelled in the packaging is
given in Table 1. Edible grade lactose, a-lactose mono-
hydrate, from Murray Goulburn Cooperative Co. Ltd.,
Melbourne, Australia, was purchased from a local
distributor.
2.2. Sample preparation
An RV10 Rising Film Vacuum Evaporator (Saurin
Technology, Melbourne, Australia), with a capacity of
10 kg evaporation per hour was used for the initial
concentration of lactose-free skim milk. The temperature
of water used to heat milk was 70 1C and condenser
temperature was 60 1C. A total of 6.2 kg lactose free skim
milk was evaporated to 1.6 kg of concentrated liquid. The
total soluble solid of the concentrated milk was measured
as 301brix.
The concentrated milk solution (301brix) was warmed to
about 50 1C and spray-dried. The spray dryer (Saurin
Technology, Melbourne, Australia) was a twin uid nozzle
type with 3 l/h water evaporation capacity. The inlet and
outlet temperatures of the dryer were set at 130 and 65 1C,
respectively. The amounts of the powder collected in
cyclone collector (cyclone recovery) and also by manual
sweeping the walls of spray dryer (sweep recovery) were
calculated. Total recovery was calculated by adding
cyclone and sweep recovery. Powder recovery was chosen
as a measure of spray drying performance as it is easily
measured with reproducible results (Bhandari, Datta,
Crooks, Rigbi, & Howes, 1997). Skim milk powder
with hydrolysed lactose (SMPHL) collected from the
outlet cyclone was immediately vacuum packed in a
Cryovac
s
plastic bag and stored in a dry chamber.
A 25 g/100 g lactose solution was also spray-dried at
180 1C inlet and 80 1C outlet temperatures.
The moisture content of the freshly spray-dried powders
was determined using AOAC method 927.05 (AOAC,
1990). Water activity of the powders was measured with an
AquaLab 3 Water Activity Metre (Decagon Devices, Inc.,
Pullman, USA) at 25 1C.
2.3. Glass transition temperature (T
g
)
Differential scanning calorimetry (DSC) (Pyris 1
equipped with Intracooler II, Perkin-Elmer 7, CT, USA)
was used to determine the glass transition temperature of
all spray-dried powders. The purge gas used was dry
nitrogen (20 mL/min). Although onset and endset T
g
values for samples were calculated in the DSC thermo-
gram, only the T
g
value determined as half DC
p
method
at half the extrapolated change in specic heat (DC
p
)
between the glassy state and the rubbery state (or
peak value) is reported in this study. Indium and zinc
(Perkin-Elmer standards) were used for temperature
and heat ow calibration. An empty aluminium pan
was used as a reference. About 510 mg samples were
scanned in hermetically sealed 50 mL DSC aluminium
pans (Perkin-Elmers). All analyses were done in triplicate.
The rate of thermal scanning was carried out in the
following order: (1) Isothermal at 20 1C for 1 min;
(2) heat scanning from 20 1C to a temperature just over
ARTICLE IN PRESS
Table 1
Composition of skim milk with hydrolysed lactose
a
Nutrients Lactose free skim milk
Energy 114 kJ (27 cal)
Protein 3.4 g
Fat 0.1 g
Carbohydrate 4.8 g
Sugars 4.8 g
Galactose 2.4 g
Lactose o0.1 g/100 g
Sodium 35 mg
Calcium 122 mg
a
Based on information given on the label.
A.K. Shrestha et al. / LWT 40 (2007) 15931600 1594
the expected T
g
at 10 1C/min; (3) cooling rapidly to 20 1C
at 50 1C/min; and (4) heat scanning from 20 to 200 1C.
The second scanning of each sample was used to reduce the
enthalpy relaxation of the amorphous powder which
appears in the rst scan, thereby enhancing the accuracy
of T
g
measurement on the DSC thermogram. The transfer
of samples from the container to the DSC pan was done in
a sealed Dry Box containing silica gel with regular N
2
ushing, to avoid unwanted moisture absorption by
the sample.
2.4. Sorption isotherm studies
The spray-dried lactose was dried overnight at 70 1C in a
vacuum oven followed by further drying in vacuum
desiccators over P
2
O
5
for a week. Considering the lower
T
g
value of hydrolysed lactose products, spray-dried
SMPHL was directly put into a P
2
O
5
containing desiccator.
To make sure the powders were fully dried, these were
further analysed for water activity and residual moisture
content. About 2 g of amorphous powders, in triplicate,
were transferred into the pre-weighed plastic cups with a
screw cap and placed in evacuated desiccators over P
2
O
5
and different saturated salt solutions of LiCl, CH
3
COOH,
MgCl
2
, K
2
CO
3
, Mg(NO
3
)
2
, KI and NaCl with respective
relative humidities of 11.4%, 23.1%, 33.2%, 44.1%,
52.9%, 68.9% and 75.3% at about 23 1C, giving a
w
of
0.01 %RH (Labuza, Kaanane, & Chen, 1985). The
samples were stored for 21 days at 2324 1C. After
equilibrium was reached, the samples were tightly closed
with the screw cap, weighed and stored in a dry glass
chamber containing silica gel until further analysis for T
g
.
The moisture content of each sample was measured.
The BrunauerEmmettTeller (BET) and Guggenheim
Andersonde Boer (GAB) equations which have previously
been used to model water sorption data for dehydrated
milk powders (Haque & Roos, 2004b; Jouppila & Roos,
1994a, 1994b; Van der Berg & Bruin, 1981) were used for
prediction of water content. The BET isotherm model
(Brunauer, Emmett, and Teller, 1938) is given by
a
w
1 a
w
m

C 1
m
o
C

a
w

1
m
o
C
. (1)
The BET isotherm was plotted a
w
/(1a
w
)m against a
w
.
In the equation, (C1)/m
o
C and 1/m
o
C form the slope
and intercept, respectively, of the straight-line equation
(Eq. (2)).
In Eq. (3), m
o
is the BET monolayer value, m and a
w
are
the equilibrium moisture content and water activity of the
product, respectively, and C is a constant related to excess
enthalpy of sorption. Calculating the values for m
o
and C
by the linear regression of the experimental data, the
moisture content (m) of the sample can be predicted by
using the following equation:
m
m
o
Ca
w
1 a
w
1 C 1a
w

. (2)
The GAB isotherm model and its second-order poly-
nomial equation as given by Van der Berg and Bruin (1981)
and Haque and Roos (2004b) are shown as follows:
m
m
o
CKa
w
1 Ka
w
1 Ka
w
CKa
w

. (3)
Second-order polynomial quadratic equation
a
w
m
aaw
2
baw g, (4)
where
a
K
m
o
1
C
1

; b
1
m
o
1
2
C

; l
1
m
o
KC
.
The solutions for the above equations were
K
b

b
2
4ag
q
2g
; C
b
gK
2,
and
m
o

1
aKC
.
The tting of BET and GAB models was checked by
calculating relative percentage root mean square (%RMS
value) as given by Haque and Roos (2004b)
%RMS

S
N
i
m
e
m
p
m
p
h i
2
r
N
100, (5)
where m
e
is the experimental moisture content and m
p
is the
predicted moisture content, and N is the total number of
experimental points.
2.5. Prediction of T
g
values using the GordonTaylor
equation
A plot of T
g
of the samples versus equilibrium moisture
content of all sorbed samples was constructed. The effect of
moisture content on T
g
values of the products was also
discussed. The GordonTaylor equation (Gordon &
Taylor, 1952) was used to model data on T
g
values for
various milk ingredients:
T
g

w
1
T
g1
kw
2
T
g2
w
1
kw
2
,
where T
g
is the predicted T
g
of a binary system, w
1
and w
2
are weight fractions of solids and water, respectively, and
T
g1
and T
g2
are the glass transition temperatures of dry
solid and water, respectively, and k is an empirical constant
for a system, i.e., 0.69 for lactose (1):water (2) system
(Saltmarch & Labuza, 1980). The T
g
value of water was
taken at 135 1C (Johari, Hallbrucker, & Mayer, 1987).
The k value for amorphous powder was determined by
averaging the k values from experimental T
g
and corre-
sponding water contents. This k value was used to predict
the T
g
of the given amorphous dairy powder (Haque &
Roos, 2004a).
ARTICLE IN PRESS
A.K. Shrestha et al. / LWT 40 (2007) 15931600 1595
3. Results and discussions
3.1. Spray drying behaviour
Considering the low T
g
value of hydrolysed lactose milk
and possible stickiness, a rather mild spray drying
condition of 130 1C inlet and 65 1C outlet temperature
was used. Only about half of the solids from the milk spray
dried could be recovered from spray drying of the lactose
free skim milk (50% total recovery). A signicant portion,
half of the total recovered powder was collected in the
cyclone collected (25% cyclone recovery), the rest of
the solids was salvaged by light manual sweeping of the
powders stuck inside wall of spray dryer, particularly
on the conical section of the dryer (25% sweep recovery).
It was noted that a large amount of powder (50%)
was rmly stuck (caked) inside the wall of the dryer
which could not be swept. The 74% recovery of lactose
in cyclone collector further demonstrated the sticky
nature of the hydrolysed lactose product. Under the
existing spray drying conditions, it is unlikely to obtain
SMPHL powder, as the products are difcult to recover
from the dryer.
3.2. Water sorption
Moisture plays important role in glass transition and
crystallization behaviour of amorphous powders that
determines its owability, stickiness and storage stability.
The experimental moisture adsorption isotherm of
SMPHL and lactose at room temperature (2324 1C) at
equilibrium after 21 days is given in Table 2 and trend is
also shown in Fig. 1. Comparison of sorption data for
SMPHL with those reported by Jouppila and Roos (1994a)
for freeze-dried skim milk with hydrolysed lactose humi-
died for 1 day showed very close results at all lower water
activities. It is interesting to note that both the samples
humidied under similar conditions for 1 and 21 days have
similar moisture content. This indicates that the SMPHL
absorb moisture quickly and are close to equilibrium
within 24 h and further humidication did not increase the
water content of the powders. The SMPHL absorbed
comparatively less water than lactose at each range of
water activity, up to a
w
X0.432. This shows spray dried
SMPHL has different water absorption capacity than those
of spray dried lactose. The sorption isotherm curve was
steeper than lactose (Fig. 1). Typically lactose started to
lose the sorbed water at a
w
X0.432 indicating signs of
crystallization. The SMPHL, however, did not lose the
sorbed water at any stage of humidication in the given
range of water activities. It indicates that crystallization in
SMPHL did not occur even for a
w
as high as 0.753.
Jouppila and Roos (1994a) also reported no crystallization
for SMPHL when stored at a
w
X0.764 but SMP crystal-
lized at a
w
X0.662 (24 h storage). However, we found that
the spray-dried SMP starts to crystallize at a
w
X0.432
when stored for a week (Shrestha, Adhikari, Howes, &
Bhandari, 2006). The result showed that the presence of
hydrolysed lactose markedly affects the water sorption
behaviour of SMP.
The BET and GAB equation were applied to model the
water sorption of SMPHL and lactose. Fig. 2 shows typical
sigmoidal adsorption isotherm curves of milk powders.
For SMPHL, moisture data was available for water
activity range up to 0.753. The predicted water content
(g H
2
O/100 g dry solid) of SMPHL was very close to the
experimental values for both BET and GAB models
(Fig. 2). The experimental values for skim milk with
hydrolysed lactose from Jouppila and Roos (1994a) also
showed very good tting with the BET and GAB models,
except at very high a
w
.
3.3. Sorption isotherm
The sorption isotherms describe the relationship between
water activity (a
w
) and the equilibrium moisture content of
a given food at a constant temperature. The sorption
isotherms can provide data about the shelf life stability of a
given food commodity. One of such parameters is the
monolayer moisture content (X
m
) which helps to dene
physical and chemical stability of foods, since it has a direct
inuence on lipid oxidation, enzyme activity, non-enzy-
matic browning, avour preservation and product struc-
ture (Labuza, Tannebaum, & Karel, 1970).
The BET and GAB monolayer moisture contents for
SMPHL were 7.72 and 8.27 g/100 g dry solid, respectively
(Table 3). The BET monolayer value for SMPHL was
lower than 9.34 g/100 g dry solid and GAB value was
slightly higher than 7.72 g/100 g dry solid as reported by
Jouppila and Roos (1994a). The difference in monolayer
moisture could be due to the use of freeze dried samples, a
shorter humidication time of 24 h and the water activity
range of 0.1140.444 for BET and 0.1140.538 for GAB
used by Jouppila and Roos (1994a). The BET and GAB
ARTICLE IN PRESS
Table 2
Glass transition temperature (T
g
) of SMPHL and lactose mixtures
humidied at different activities
a,b,c
Water activity SMPHL Lactose
Water (%) T
g
(1C) Water (%) T
g
(1C)
0 0.0 47.773.8 0.0 97.875.5
0.113 1.770.2 26.273.2 2.270.0 82.271.8
0.225 3.970.0 9.372.1 4.670.1 57.872.0
0.328 5.670.1 3.571.3 6.770.0 46.772.6
0.432 8.170.0 NA
d
9.870.2 23.970.5
0.529 11.170.3 NA 4.070.1 10.772.4
0.689 20.270.3 NA NA NA
0.753 26.170.7 NA NA NA
a
Mean values7standard deviation of triplicate samples.
b
Moisture is presented as g H
2
O/100 g dry solid.
c
For glass transition temperature only mid-point values are reported.
d
Not analysed.
A.K. Shrestha et al. / LWT 40 (2007) 15931600 1596
ARTICLE IN PRESS
Fig. 2. Water sorption isotherm of SMPHL (A) and lactose (B) humidied for 3 weeks at various water activities at 23 1C using experimental data (),
BET predicted (), GAB predicted (m) and from Jouppila and Roos (1994a) (K).
Fig. 1. Moisture contents and glass transition temperatures of SMPHL and lactose humidied for 3 weeks at various water activities at 23 1C: T
g
of
SMPHL (), T
g
for lactose (K), moisture for SMPHL (~) and moisture for lactose (m).
Table 3
Constants for the sorption isotherm models, GAB and BET, including monolayer moisture content
a
Samples a b g X
m
c
K c R
2
%RMS
d
GAB model
SMPHL 0.055 0.008 0.066 8.27 0.97 1.87 0.98 1.14
Lactose 0.102 0.041 0.047 6.96 1.10 2.81 0.997 0.24
Lactose
b
0.149 0.667 0.045 4.77 1.589 2.93 0.984 0.29
Samples b c K X
m
R
2
%RMS
BET model
SMPHL 0.064 0.065 1.99 7.72 0.865 1.98
Lactose 0.074 0.048 2.533 8.160 0.997 0.25
Lactose
b
0.076 0.050 2.492 8.026 0.982 0.88
The meaning of above notations is explained in Materials and methods section.
a
Water activity range of 0.113oa
w
40.432 selected for lactose and SMPHL.
b
Data from Haque and Roos (2004a) to compare the results.
c
X
m
Monolayer moisture content, g H
2
O/100 g dry solid.
d
RMS root mean square value.
A.K. Shrestha et al. / LWT 40 (2007) 15931600 1597
monolayer values for lactose were 8.16 and 6.96 g/100 g dry
solid, respectively. The available data on monolayer values
for lactose vary widely: 6.29 for BET and 4.91 for GAB
(Jouppila & Roos, 1994a); 6.26 for BET (Jouppila & Roos,
1997); 6.93 (at 12 1C) and 4.9 (at 2038 1C) for GAB
(Bronlund & Paterson, 2004); and 8.03 for BET and 4.77
for GAB (Haque & Roos, 2004a). It shows the monolayer
value for amorphous lactose varies depending on the
method of sample preparation; humidication techniques:
storage time and temperature; water activity range used,
etc. The monolayer moisture content values (X
m
) indicated
the hydrolysed lactose milk powder is fairly stable at
moisture content of about 8 g/100 g dry solids, and above
this critical moisture content, the stability of the powders
will be low.
Table 3 shows the BET and GAB parameters including
%RMS and R
2
values for lactose and SMPHL. Data from
Haque and Roos (2004a) is also included to compare the
lactose results. The %RMS values of SMPHL for GAB
and BET models were calculated as 1.14 and 1.98,
respectively, whereas for lactose both models gave almost
similar values of about 0.25. The regression coefcients of
both models were closer to unity, except for BET model in
SMPHL which is low at 0.865. This indicates that GAB
model is better tted for these powders that BET model.
3.4. Glass transition temperature (T
g
) of SMPHL and
lactose
The T
g
values of spray-dried SMPHL and lactose at
corresponding moisture contents are given in Table 2 (and
Fig. 1). The T
g
value of SMPHL in dry state was 48 1C
which is less than the value for dry lactose, 97.8 1C and dry
skim milk powder or SMP at 93 1C (Shrestha et al., 2006).
Similarly, T
g
values of the SMPHL were less than lactose
when measured at other water activities (and moisture
contents). Jouppila and Roos (1994b) reported a T
g
value
of 49 1C for anhydrous hydrolyse lactose skim milk powder
which is very close to the present result. Fernandez et al.
(2003) measured the T
g
values of whole milk powder with
partially hydrolysed lactose (0.6 g H
2
O/100 g, and lactose,
glucose, galactose ratios of 8:15:15) and also a mixture of
lactose, glucose and galactose (22:39:39). They reported a
T
g
value of about 58 1C for hydrolysed whole milk powder
(moisture about 0.6 g/100 g). The T
g
values of pure glucose
and galactose are 30 and 31 1C, respectively (Roos, 1993;
Roos & Karel, 1991a). The low T
g
value of the SMPHL
compared to SMP was due to the presence of glucose and
galactose in SMP. The higher T
g
value (431 1C) of
SMPHL suggests the presence of residual unhydrolysed
lactose, more than the label claim of o0.1% in milk or
about 1% on a dry basis. Jouppila and Roos (1994b)
and Fernandez et al. (2003) also reported a higher T
g
value for freeze dried SMPHL and suggested that residual
unhydrolysed lactose might have increased the T
g
of
the mixture.
The T
g
values of SMPHL decreased signicantly
with increase in moisture content. Table 2 shows that
even a slight absorption of water by dehydrated SMPHL
(1.7 g/100 g dry basis) almost halved the T
g
value. Even at
moderately low humidity (23.8%RH), the T
g
value of
SMPHL was below 0 1C (Table 2). Interestingly the powder
remained more or less free owing under the ambient
condition which is most likely to be contributed by the milk
proteins. SMP contains signicant amounts of proteins
(3437 g/100 g) that can affect the water sorption and
crystallization behaviour lactose in the protein lactose
matrix. It has been well established that incorporation of
high molecular weight compounds that have high T
g
have
ability to raise the T
g
value of the material containing low
T
g
compounds (Bhandari et al., 1997; Roos & Karel,
1991b). This study further veried our previous nding
that proteins form incompatible mixture with the sugar
compounds and do not inuence the T
g
value (Shrestha,
Adhikari, Howes, & Bhandari, 2005), which, in present
case, is solely contributed by residual and hydrolysed
lactose compounds. The role of (milk) proteins in retarda-
tion of crystallization and subsequent stickiness and caking
of lactose in milk powder is not known and warrants
further research.
The suitability of DSC as a technique to measure T
g
of
protein-rich milk powders is questionable. In previous
study we observed that the endothermic peak associated
with glass transition of high protein (low lactose) becomes
broader with increase in protein concentration and no
peaks can be seen if protein level is too high (Shrestha
et al., 2005). The Spray Drying Research Group at The
University of Queensland, Brisbane, Australia, has recently
developed a technique based on thermal mechanical
compression test to measure glassrubber transition
temperature, T
gr
(Boonyai, Howes, & Bhandari, 2005).
It consistently gave higher transition temperature when the
level of protein in amorphous solid increased (Shrestha
et al., 2006). Therefore, to analyse the mechanical
behaviour of the powder (such as stickiness and ow-
ability), this technique can be more useful than the DSC
technique.
3.5. Critical water content and storage conditions
The critical water content/water activity is the value
when the glass transition temperature of the product equals
to the room temperature (which is assumed to be around
23 1C in this work). All amorphous products are meta-
stable, and therefore are liable to caking and crystallization
over time during storage (Bhandari & Howes, 1999).
Stability of the amorphous products is largely dictated by
the T
g
which in turn depends on storage conditions such as
water activity or humidity and temperature (Roos & Karel,
1990; Slade & Levine, 1991). This is more important in low
molecular products and protein hydrolysates which are
highly hygroscopic (Aguilera, Delvalle, & Karel, 1995).
The sorption data for SMPHL and lactose was obtained by
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A.K. Shrestha et al. / LWT 40 (2007) 15931600 1598
tting moisture data into BET equation (model). The T
g
values at the given a
w
and water content were predicted by
GordonTaylor equation. As expected the T
g
values
decreased with increase in storage a
w
or moisture content
due to plasticizing effect of water on the amorphous
components (Fig. 3). The critical a
w
for SMPHL was 0.15
at a storage temperature of 23 1C for 3 weeks. The water
content of the SMPHL under these conditions was 2.4 g/
100 g dry solid. In comparison, pure lactose stored under
similar conditions had critical a
w
of 0.39 and water content
8 g H
2
O/100 g dry solid. The critical storage conditions for
SMPHL or SMPHL and lactose mixtures were very close
to the values reported by Jouppila and Roos (1994b).
The lower critical a
w
and water content clearly indicated
the vulnerability of SMPHL under processing, handling
and storage conditions. The product would be difcult to
dry as the conditions of outlet air humidity and tempera-
ture of the spray dryer would be closer or higher than the
critical conditions. Since the T
g
of SMPHL is so low, the
molecular mobility of the solid will be high even at room
temperature which might have led to deteriorative changes
such as structural collapse, stickiness and caking. Experi-
mentally spray drying of lactose-free skim milk showed a
large amount of the powder got sticky and could not be
recovered. The outlet temperature of dryer was 60 1C and
the powder had a
w
about 0.1, which is higher than T
g
value (49 1C) of anhydrous SMPHL.
Glucose and galactose, the major components of
hydrolysed lactose, have low glass transition temperatures
and at higher storage temperature may react with protein
present in the powder causing non-enzymatic browning.
One of the interesting aspects of SMPHL was the water
content kept on increasing with increasing storage a
w
unlike lactose that started to release water at a
w
X0.432 and
start to absorb water again a
w
X0.529, due to crystal-
lization. There was no visible crystallization in SMPHL
like lactose. No crystallization peaks were seen when
SMPHL was scanned through DSC. SMP has a signicant
amount of protein in its matrix, about 34 g/100 g. It
appears that protein delays or masks the crystallization
of glucose, galactose and residual lactose.
4. Conclusions
Spray drying of SMP with hydrolysed lactose is difcult
as most of the powder stuck inside the dryer even at very
low inlet/outlet air temperatures. This is due to the low
glass transition temperature of glucose and galactose, two
major components of hydrolysed lactose. SMPHL ab-
sorbed less water than lactose when stored under similar
%relative humidity and did not show any sign of crystal-
lization of sugars even at higher water activity. The
sorption isotherm data for SMPHL tted well into BET
and GAB models with monolayer moisture contents of
7.55 and 8.27 g/100 g, respectively. The stability of SMPHL
was much lower than lactose as shown by low critical
values for a
w
and water content in state diagram. These
data can be used to assess the proper spray drying
condition, stickiness and storage behaviour of SMPHL.
Acknowledgement
This research was nancially supported by Dairy
Ingredients Group of Australia (DIGA), Melbourne,
Australia (Project No. UQ3412).
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Fig. 3. Relationship between the water activities at 23 1C, water content (m) and glass transition temperature, T
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