Journal of Food Engineering 99 (2010) 7682

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Journal of Food Engineering

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

A novel technique for determining glassrubber transition in dairy powders

S.A. Hogan a,*, M.H. Famelart b, D.J. OCallaghan a, P. Schuck b
a
Department of Food Processing and Functionality, Teagasc, Moorepark Food Research Centre, Fermoy, Co. Cork, Ireland
b
UMR 1253 Science et Technologie du Lait et de lOeuf, Inra-Agrocampus Ouest, 65 Rue de St-Brieuc, 35042 Rennes Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: A novel rheological technique is described, for determining the glassrubber transition temperature (Tgr)
Received 19 November 2009 of spray dried dairy powders. The approach involves constant rate heating of powder under compression
Received in revised form 27 January 2010 and measurement of changes in either gap distance (Method 1) or normal force (Method 2). Signicant
Accepted 28 January 2010
increases in the rate of change of these parameters was shown to correspond with Tgr. The techniques
Available online 4 February 2010
were applied to skim milk, micellar casein and whey permeate powders and a range of fat-enriched
micellar casein powders. Tgr temperatures, so obtained, were compared with glass transition tempera-
Keywords:
tures (Tg) determined by Differential Scanning Calorimetry (DSC). Methods 1 and 2 gave predictions
Spray dried powders
Glassrubber transition
for non-fat dairy powders of Tg endset (Tge) with SEP of 8.8 and 4.4 C, respectively. These novel tech-
Rheometer niques provide an accurate means of determining glass transitions in dairy powders, including high pro-
Differential scanning calorimetry tein and fat-containing powders, whose relaxation properties can be difcult to measure by DSC.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
The stability of dairy powders is closely associated with the
physical state of their constituents. Food powders containing
amorphous materials, such as lactose, can undergo physical
changes such as sticking, caking, collapse and crystallisation, which
ultimately impact on quality and functionality. This paper de-
scribes a novel technique for measuring an index of such structural
changes.
It is well established that physical changes in food powders are
related to the glass transition phenomenon (Chuy and Labuza,
1994; Roos, 1995). The glass transition temperature (Tg) of a super-
saturated, amorphous material, refers to a temperature range over
which the material changes from a glassy (solid-like) to a rub-
bery (liquid-like) form. Below Tg, the material can be considered
to exist in a pseudo-equilibrium condition and although thermody-
namically metastable, can be stored for extended periods without
signicant physical change. At and above Tg, increased molecular
mobility and decreased viscosity result in a softening of particle
surfaces leading to the deteriorative changes outlined above.
In terms of composition, low molecular weight or chain length
molecules tend to be more exible and have lower Tg values. Car-
bohydrates, particularly low molecular weight sugars, have a sig-
nicant effect in depressing Tg (Bhandari and Howes, 1999) and
tend to dominate physical changes observed in dairy powders
(Roos, 2002). High molecular weight food polymers such as poly-
* Corresponding author. Tel.: +353 25 42455; fax: +353 25 42340.
E-mail address: sean.a.hogan@teagasc.ie (S.A. Hogan).
saccharides and proteins have high Tg values and are considered
stable.
Water acts as a plasticising, or softening agent, in amorphous
food materials and has an exponential effect in lowering Tg such ef-
fects may be due to shielding of attractive, inter- and intra-molec-
ular interactions and by decreasing the activation energy of
molecular motion (Matveev et al., 2000). Pure water has a very
low Tg of 135 C (Johari et al., 1987) and hence, because of the
additive effect of components, has a major effect in lowering the
overall Tg of dairy powders.
Measurement of state transitions in food systems is done using
thermal and mechanical techniques, such as differential scanning
calorimetry (DSC), dynamic mechanical analysis (DMA) and ther-
mal mechanical analysis (TMA). In DSC, Tg is characterised by mea-
surable discontinuity in specic heat capacity. DMA, in contrast,
applies an oscillating force to the material and the resultant
changes in storage and loss moduli, as a function of temperature,
allow determination of glass transition. TMA measures dimen-
sional changes in materials as a function of temperature and de-
nes glass transition in terms of the change in the coefcient of
expansion as the material changes from glass to rubber. Transitions
may be more easily observed using one technique compared to an-
other depending on the material.
In recent years several alternative approaches to measurement
of state transitions have been developed. A static mechanical com-
pression test for measuring glassrubber transitions in skim milk
powder was developed by Boonyai et al. (2005, 2007). The device
comprised a thermally-controlled sample cell used in conjunction
with a texture analyser to determine the glassrubber transition
temperatures of skim milk powder. Bengoechea et al. (2007) used

0260-8774/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2010.01.040
 S.A. Hogan et al. / Journal of Food Engineering 99 (2010) 7682
phase transition analysis (PTA) to determine the transition temper-
ature of a range of food protein powders. This technique involves
application of pressure to the sample by means of a piston. The
glass transition temperature was identied as the point at which
the material softens, thereby allowing increased movement of
the piston. Phase transition results obtained by this method were
consistent with those measured by DSC, DMTA and capillary
rheometry.
The objective of this study was to develop a means by which the
Tgr of spray dried dairy powders could be determined using stan-
dard laboratory rheological equipment and to establish the efcacy
of such techniques for the determination of Tgr in a range of dairy
powders differing in composition and water activity. The technique
described by Boonyai et al. (2005, 2007) was adapted without re-
course to customised equipment. The precision and control of a
modern rheometer with air or magnetic bearings allowed further
development of the technique, leading to two distinct methods
which were compared with DSC measurements.
2. Materials and methods
2.1. Materials
Hardened coconut oil (Ertilor C 32/34) was purchased from Fuji
Oil Europe (Gent, Belgium). This vegetable oil is commonly used in
fat-lled dairy powders. Micellar casein (Promilk 872 B) was pur-
chased from Ingrdia (Arras, France), whey permeate powder
was purchased from Kerry Group plc. (Tralee, Ireland) and edible
lactose from Lactoserum France (Baleycourt, France). Skim milk
powder was produced at Bionov (Rennes, France) according to
Schuck et al. (1994).
2.2. Preparation of emulsions
For the fat-enriched micellar casein powder, micellar casein
(dry matter (DM) content 200 g/kg) was dissolved in hot water
(60 C) and stirred for 2 h in a 300 L tank. The optimal dissolution
of the powder was assessed by laser light-scattering measure-
ments. Melted, hardened coconut oil (60 C) was then added at
100 and 400 g/kg dry matter to the micellar casein solutions. Lac-
tose and water was also added to the micellar solution to standard-
ize the total nitrogen (TN) at non-fat solids content of 90%, 35% and
15%. Final solids content was 200 g/kg in the ve resulting mix-
tures. The mixtures were stirred gently for 15 min before process-
ing and maintained at 60 C throughout the experiment
(180 min). Mixtures were homogenized at 16 and 4 MPa, for rst
and second stages, respectively, using an APV Rannie LAB 12/51 H
homogenizer (Assistance Techniques Spciales, Moissy Cramayel,
France). The ow rate was 100 L/h.
2.3. Spray-drying of emulsions and storage of powders
Emulsions were immediately dried in a pilot-scale multistage
spray dryer (GEA-PE, St Quentin en Yvelines, France) at Bionov (Re-
nnes, France). The evaporation rate was 70100 kg/h. A high-pres-
sure pump fed the emulsion to the drying chamber at a ow rate of
100 L/h. The spray-dryer operated concurrently and had a spray
nozzle with an orice of 0.73 mm in diameter. Inlet air humidity
was controlled and adjusted by a dehumidier (Munters, Sollent-
una, Sweden) at 1 g/kg of water in dry air. Inlet and outlet gas tem-
peratures were 190 and 90 C, respectively. Powders were
agglomerated by recycling ne particles from the cyclone to the
top of the drying chamber and collected in 25 kg paper bags at
temperatures ranging from 20 to 30 C. Powders were stored, in
77
the dark, at a controlled temperature of 20 C, in sealed bags under
low-vacuum conditions.
2.4. Chemical and physical analyses
Free water content was calculated by weight loss after drying
5 g of the samples with sand in a forced air oven at 105 C for
5 h. Water activity (aw) was measured using a water activity-meter
(aw-meter; Novasina RTD 200/0 and RTD 33, Pffkon, Switzer-
land) at 20 C. Working moisture adsorption isotherms were
determined using the method proposed by Mauer et al. (2000).
Approximately 20 g samples of dairy powders were weighed into
stainless steel dishes and placed in desiccators containing the fol-
lowing saturated salt solutions: LiCl, CH3COOK, MgCl2 and NaI with
relative humidities (RH) of 11, 22, 33 and 38 (2% RH) respectively,
giving aw values of 0.01  percentage equilibrium RH (Mauer et al.,
2000). The desiccators were then placed in temperature controlled
chambers at 20 2 C, and samples were allowed to equilibrate for
15 d. Preliminary experiments showed that the dairy powders
reached equilibrium, either by adsorption or desorption, within
10 d. However, to ensure a constant aw, dairy powder samples
were equilibrated for 15 days prior to use. Glass transition temper-
atures (Tg) and heat capacity changes (DCp) were determined by
differential scanning calorimetry (DSC) (Q-1000, TA Instruments,
Saint Quentin en Yvelines, France) calibrated with indium (melting
point 156.6 C). The samples were scanned twice to eliminate the
hysteresis effect of thermal relaxation typical of glass transitions.
The initial scanning rate was 5 C min1 from 20 to +70 C. Sam-
ples were cooled at 10 C min1 to 20 C, and the Tg range was
determined from the DSC curve of the second scan at 5 C min1
from 20 C to +140 C, giving three values: Tg onset (Tgo), Tg mid-
point (Tgm) and Tg endset (Tge). DCp values were established by the
change in heat capacity between Tgo and Tge.
2.5. Glassrubber transitions
Glassrubber transitions were determined, using a laboratory
rheometer (AR2000, TA Instruments UK, Ltd., Crawley, England)
by two methods involving compression of a powder sample (ca.
2 g) between a 40 mm steel parallel plate and a Peltier plate. Small
amplitude shear oscillation (0.1 lN m at 25 Hz) was applied in or-
der to promote even distribution of the powder sample. In Method
1, the gap between plates was measured under a constant normal
force of 30 N, loosely analogous to a creep test. In Method 2, nor-
mal force was measured at a constant gap following initial com-
pression to 30 N, loosely analogous to a stress relaxation test.
Gap distance (Method 1) or normal force (Method 2) was recorded
while the temperature of the sample was raised, using the Peltier
plate, from 20 to 100+ C at a rate of 2 C/min, after an initial equil-
ibration time of 10 s. A gap temperature compensation factor of
0.5 lm/C was used to allow for thermal expansion of the steel
plate. Tgr was identied by a signicant increase in the rate of
change in gap distance (Method 1) or normal force (Method 2).
3. Results and discussion
3.1. Powder compositions
The non-fat powders examined included powders with a wide
range of protein and lactose contents (Table 1). Protein contents
ranged from 89.1% to 0.7% for micellar casein and whey permeate
powders, respectively. It was assumed, with the exception of whey
permeate powder, that lactose existed in the amorphous state fol-
lowing spray drying (Roos, 1995). In the case of whey permeate
powder, lactose was pre-crystallised prior to spray drying, in order
78 S.A. Hogan et al. / Journal of Food Engineering 99 (2010) 7682

Table 1
Composition of non-fat powders following spray drying.

Protein (g/100 g) Moisture (g/100 g) Ash (g/100 g) Lactose (g/100 g)a

Micellar casein 82.1 2.1 8.6 0.1 7.5 0.3 1.9
SMP 33.6 0.6 3.8 0.2 7.7 0.2 54.9
Whey permeate 0.66 0.1 2.3 0.09 8.1 0.2 89.0
a
Lactose was determined by difference.

to minimise sticking and caking of powders during drying, trans-
port and storage. The % crystallinity of this powder was estimated
at 80 3%, according to the method of Schuck and Dolivet (2002).
Fat in these types of powders is normally present at very low levels
(<1%) and was not considered signicant with regard to measure-
ment of glassrubber transitions.
Micellar casein contents of fat-containing (10% or 40% fat) ran-
ged from 52.0% to 8.7% for Powders 1 and 5, respectively and lac-
tose contents were in the range 069.3%. Protein/lactose ratios
were similar in Powders 2 and 3 (0.58 and 0.62, respectively)
and Powders 4 and 5 (0.19 in each case) (Table 2).
3.2. Moisture sorption
Moisture contents of micellar casein (MC) powders ranged from
2.1% to 9.1% for aw of 0.10.4 respectively and were the highest of
the powders examined (Table 2). Moisture contents of MC powder
were similar to a high micellar casein powder (84% casein) re-
ported by Foster et al. (2005) at equivalent RH but lower than those
of a native phosphocaseinate powder reported by Schuck et al.
(2005). The more hygroscopic nature of the MC powder compared
to the other powders is supported by previous ndings (Schuck et
al., 2005).
Whey permeate (WP) powders had the lowest moisture con-
tents due to the presence of crystalline lactose, which sorbs much
less water than the amorphous form (Bronlund and Paterson,
2004). The moisture contents of permeate powder were lower than
those reported by Schuck et al. (2005) for pre-crystallised whey
powder, which had a lower percentage of lactose in the crystalline
form (70% vs. 80% in this study).
3.3. Glassrubber transitions
3.3.1. Non-fat powders
Both rheological methods were capable of determining a glass
rubber transition in the non-fat dairy powders examined (Table 3).
Tgr was determined by extrapolation, to the temperature axis, of
the intersect between pre- and post-inection areas of the curve
(Fig. 1). In all powders, increases in free moisture content resulted
in a decrease in Tgr values, due to the effects of plasticisation by
water in lowering transition temperatures in amorphous materials
(Roos and Karel, 1991; Slade and Levine, 1991). Such effects are ex-
pected, as water is a very signicant and ubiquitous plasticiser of
most biological materials (Gunasekaran and Mehmet Ak, 2000).
Representative Tgr curves for SMP, determined by Methods 1
and 2 showed clear inections due to the transition from the glassy
to the less viscous, rubbery state (Fig. 1). With Method 1 it could be
observed that the rate of change in gap distance at the transition
point, and the overall extent of deformation, was more pronounced
in powders with increasing moisture content. This difference can
be ascribed to the plasticising effects of moisture combined with
decreasing viscosity of surfaces, and ultimately of the bulk mate-
rial, as temperature increases beyond Tgr. In the case of Method
2, powders showed a clearly dened inection around the glass
rubber transition regardless of moisture content. This suggests that
Method 2 was more sensitive than Method 1 with regard to state
changes in low moisture SMP powders.
The effects of moisture content on the shape of Tgr curves of MC
powders (Fig. 2) was broadly similar to that of SMP powders
although the extent to which gap distance (Method 1) or normal
force (Method 2) changed around Tgr was less pronounced, partic-
ularly in powders with low moisture content. The Tg and Tgr tem-
peratures observed for MC, equilibrated at aw 0.40, were lower
compared to DSC, DMTA and PTA measurements reported by Ben-
goechea et al. (2007), at a similar moisture content, and lower also
than the DSC measurements of Schuck et al. (2005) for native phos-
phocaseinate powders.
Tgr values for WP powders, equilibrated at low aw, determined
by Method 1 were characterised by relatively small changes in
gap distance and a rather subtle inection (Fig. 3). Again, changes
in gap distance, around the transition, were more apparent in pow-
ders with higher moisture contents. Tgr curves for WP powders
determined by Method 2 were more pronounced than Method 1
and showed an increase in normal force prior to the glassrubber
transition. Similar effects were observed, albeit to a lesser extent,
in SMP and micellar casein powders equilibrated under low RH
conditions and may have been due to expansion of interstitial or
occluded air in powder particles upon heating. Powders with high-
er moisture may have been less prone to such expansion. Equiva-
lent increases in gap distance were not observed in powders
determined by Method 1, presumably because of compression un-
der a constant normal force. Tg values of WP powders were similar
to those reported by Schuck et al. (2005) for pre-crystallised whey
powders stored under equivalent RH conditions.
3.3.2. Fat-enriched micellar casein powders
Measurement of Tg by DSC in fat-containing dairy powders may
not be possible where the dominant fat melting endotherm

Table 2
Composition of fat-enriched micellar casein powders.

Powders (g/100 g) Moisture (g/100 g) Protein (g/100 g) Fat (g/100 g) Ash (g/100 g) Lactose (g/100 g)a P/L (g/100 g)
Powder 1 3.5 1 52.0 3 39.5 5 5.2 1 0 N/Ab
Powder 2 5.9 1 30.3 2 10.2 2 2.7 0 50.9 0.58
Powder 3 3.6 1 20.9 2 39.8 7 2.0 0 33.7 0.62
Powder 4 4.4 1 13.3 1 11.7 2 1.3 0 69.3 0.19
Powder 5 3.4 2 8.7 0 41.2 4 9.0 0 45.8 0.19
a
Lactose content determined by difference.
b
Not applicable.
 S.A. Hogan et al. / Journal of Food Engineering 99 (2010) 7682 79

Table 3
Comparison of glassrubber transition temperatures (Tgr) of non-fat powders, determined using rheometer methods, with glass transition temperature (Tg), as determined by
DSC.

Powder aw Moisture content Rheology DSC

() (%) Tgr Method 1 (C) Tgr Method 2 (C) Tg onset (C) Tg midpoint (C) Tg endset (C) DCp (J/g/C)
n=3 n=3 n=3 n=2 n=2
Micellar casein 0.10 0.01 2.1 0.1 104 2 88 2 83 5 85 4 95 4 0.09 0.03
0.11 0.01 3.1 0.1 96 2 72 2 58 3 65 3 70 2 0.18 0.03
0.40 0.01 9.1 0.2 65 2 59 2 51 2 56 3 60 2 0.27 0.01
Skim milk 0.10 0.01 1.9 0.2 89 2 71 2 61 2 64 2 71 2 0.27 0.01
0.15 0.01 3.9 0.1 68 2 54 2 46 1 48 2 54 2 0.28 0.01
0.38 0.02 8.1 0.2 31 2 20 2 11 2 15 1 20 2 0.16 0.01
Whey permeate 0.10 0.01 1.0 0.1 114 3 79 2 70 2 75 2 80 2 0.16 0.02
0.16 0.01 1.9 0.1 66 2 58 1 39 1 46 1 52 2 0.17 0.01
0.39 0.02 3.6 0.2 28 2 22 2 12 2 16 1 21 1 0.12 0.01

4700
5000
A
A
4600
4500

Gap distance, m
Gap distance, m

4500
4000

4400
3500

3000 4300

2500 4200
20 40 60 80 100 120 140 20 40 60 80 100 120 140

Temperature, C Temperature, C

40 40
B 35
B
35
30
30
Normal force, N

25
Normal force, N

25
20
20
15
15
10
10
5
5
0
0
-5
10 20 30 40 50 60 70 80 90 100 110 120 130 140
20 40 60 80 100 120 140
Temperature, C
Temperature, C
Fig. 1. Representative Tgr curves for SMP, determined by Method 1 (A) and Method
2 (B). Powders, equilibrated at aw 0.10 ( ), 0.15 ( ) and 0.38 ( ), had Fig. 2. Representative Tgr curves for micellar casein powders, determined by
moisture contents of 1.9%, 3.9% and 8.1%, respectively. Arrows indicate position of Method 1 (A) and Method 2 (B). Powders, equilibrated at aw 0.10 ( ), 0.11 ( )
Tgr. and 0.40 ( ), had moisture contents of 2.1%, 3.1% and 9.1%, respectively. Arrows
indicate position of Tgr.

overlaps with Tg (Joupilla and Roos, 1994; Vuataz, 2002). The coin-
cidence of these transitions is dependent on the melting range of
the fat and moisture content of the powders (which is the major
determinant of Tg for any given powder). Due to this overlap, deter-
mination of Tg by DSC was possible in only two of the ve fat-con-
taining powders examined (Table 4). In contrast, Tgr appeared to be
measurable in all powders by both rheological methods developed
in this study. Fat melting endotherms were evident in all DSC ther-
mograms (Fig 4). Tgr curves were similar in appearance to those ob-
tained for the non-fat powders already discussed. It was assumed,
therefore, that the transitions observed were due to thermal plas-
ticisation of non-fat components only. To the best of our knowl-
edge no comparative data is available on mechanical relaxations
in fat-containing dairy powders.
3.4. Comparison of rheometer methods
Forcedeformation characteristics of a material can be deter-
mined by either creep or stress relaxation tests. The former may
80 S.A. Hogan et al. / Journal of Food Engineering 99 (2010) 7682

3000 -0.04
2900
A Fat melting
-0.06 Tg
2800
Gap distance, m

Powder 5
2700 -0.08 Powder 2

Heat flow, W/g

2600
-0.1 Powder 1
2500
2400
-0.12
2300
2200 -0.14
2100
2000 -0.16
20 40 60 80 100 120 140
Temperature, C -0.18
0 10 20 30 40 50 60 70
45 Temperature, C
40 B
Fig. 4. Representative DSC thermograms of fat-enriched micellar casein powders.
35 Fat melting endotherms were visible in all powders. Of the ve powders
investigated, denitive Tg endotherms could only be determined in Powders 4
Normal force, N

30 and 5.

25

20
15
10
5 spicuous in powders with low moisture content.
0 Values for Tgr determined by Method 2 were lower, in all cases,
20 40 60 80 100 120
Temperature, C
Fig. 3. Representative Tgr curves for whey permeate powders, determined by
Method 1 (A) and Method 2 (B). Powders, equilibrated at aw 0.10 ( ), 0.16 ( )
and 0.39 ( ), had moisture contents of 1.0%, 1.9% and 3.6%, respectively. Arrows
indicate position of Tgr.
be dened as deformation that occurs over a period of time when a
material is subjected to constant stress at constant temperature. In
the present study, Method 1 may be considered as equivalent to a
non-isothermal creep test, in which the effects of constant stress
on material deformation are recorded as a function of temperature.
In contrast, a stress relaxation test involves a decrease in stress
in a material subjected to constant strain at a constant tempera-
ture. Method 2 may therefore be considered as equivalent to a
non-isothermal stress relaxation test, in which the effects of con-
stant strain on material deformation are recorded as a function
of temperature.
Boonyai et al. (2007) suggested that changes in displacement
associated with creep tests can be more sensitive than the amount
of force reduced during a stress relaxation test. In terms of compar-
ison between the dependent variable response of the two methods
examined in this study, glassrubber transitions determined by
Method 2 were more pronounced than Method 1 and were con-
140 than for equivalent powders determined by Method 1 (Table 2)
and were closer to Tg values determined by DSC. It is possible that
Method 2 facilitates the onset of molecular motion around the
transition and requires a lower thermal activation energy for the
transition to occur. Given, however, the multi-factorial nature of
such measurements the reasons for the differences in Tgr between
Methods 1 and 2 are not readily identiable. Application of a con-
stant normal force (as in Method 1) might delay the onset of Tgr in
the same way that application of higher frequencies delays transi-
tions in materials determined by DEA and DMA (Talja and Roos,
2001). Boonyai et al. (2007) reported that glassrubber transitions
in SMP, measured by a thermal mechanical compression test, not
dissimilar to Method 1, occurred at lower temps than DSC and
TMA.
Both Tgr methods were more closely correlated with Tge than Tgo
or Tgm temperatures. Coefcients of determination between Meth-
od 2 and Tge (Fig. 5) were greater than for equivalent powders
determined by Tgr Method 1, (P < 0.01) based on analysis of resid-
uals using F test. In the non-fat powders examined, standard errors
of prediction of Tgr, by Methods 1 and 2, calculated by least squares
regression of Tgr by each respective method against Tge, were 8.8
and 4.4 C, respectively.

Table 4
Comparison of glassrubber transition temperatures (Tgr) of fat-containing powders, determined using the rheometer methods developed, with glass transition temperature (Tg),
as determined by DSC.

Powder aw Moisture content Rheology DSC

() (%) Tgr Method 1 (C) Tgr Method 2 (C) Tg onset (C) Tg midpoint (C) Tg endset (C)
n=3 n=3 n=3 n=2 n=2
1 0.19 0.00 3.5 0.1 69 1 39 2 nda nd nd
2 0.32 0.00 5.9 0.1 40 2 34 1 nd nd nd
3 0.28 0.01 3.6 0.1 39 1 29 2 nd nd nd
4 0.32 0.00 4.4 0.1 40 2 34 1 31 2 33 1 35 1
5 0.27 0.00 3.4 0.2 57 1 43 1 45 2 47 1 49 1
a
Tg could not be determined due to overlap of fat melting and glass transition endotherms.
 S.A. Hogan et al. / Journal of Food Engineering 99 (2010) 7682
120
Method 1
100 y = 1.178x + 5.1035
2
R = 0.9177
80
T gr, C
o
60
Method 2
40 y = 0.9287x + 3.9547
2
R = 0.9668
20
0
0 20 40 60 80
o 0
Tge, C
Fig. 5. Inuence of method on the correlation between glassrubber transition (Tgr)
and Tge (endset), as determined by DSC.
3.5. Nature of the transition
Difculties in determining glass transition temperature of pro-
teins have been previously reported (Bhandari and Howes, 1999;
Roos, 1995). Experimental data on Tg of proteins are quite limited
(Matveev et al., 1997) and mostly refer to proteins plasticised by
water (Kalivchesky et al., 1993; Mauer et al., 2000) as anhydrous
high molecular weight polymers tend to decompose before Tg is
reached (Roos, 1995). Transitions in such materials are broad and
tend not to be characterised by signicant changes in DCp. In poly-
mer systems, DCp can be small and therefore difcult to determine
by DSC (Mauer et al., 2000).
In the present study, DCp of MC powders equilibrated at aw 0.10
was very low (0.09 J/g/C) but was greater in powders equilibrated
at higher aw. Zhou and Labuza (2007) also reported very low DCp
values for whey protein isolate and b-lactoglobulin. The increase
in DCp with increasing moisture content contrasts with the nd-
ings of Mauer et al. (2000) but is consistent with those of Schuck
et al. (2005) with regard to the effects of moisture on DCp of dairy
protein powders. Values for DCp at equivalent moisture contents
i.e. 2.1%, 1.9% and 1.9% for MC, WP and SMP were 0.09, 0.17 and
0.27 J/g/C, respectively. Schuck et al. (2005) suggested that, in
dairy powders, DCp is largely determined by the amount of amor-
phous lactose present. The value for WP was lower than SMP be-
cause, despite having a higher overall lactose content, only ca.
20% of the lactose was present in the amorphous form and it is this
fraction that undergoes a glass transition. The drop in DCp ob-
served in SMP and permeate powders at aw 0.39 may be indicative
of the onset of crystallisation of amorphous lactose, which is
known to occur at around this aw (Joupilla and Roos, 1994).
Angell (1985) developed a scheme that classies liquids as
strong or fragile according to the dependence of viscosity on
Tg/T. Strong materials, such as high protein powders generally
have a small DCp at Tg. In contrast fragile materials, such as pow-
ders containing amorphous lactose, have a large DCp and show
greater changes in viscosity around Tg. Changes in moisture con-
tent of fragile powders will tend therefore to have greater conse-
quences with regard to material relaxation and subsequent
functional changes such as sticking and caking.
The complex relationship between Tgr and moisture content for
different dairy powders is illustrated in Fig. 6. Mechanical transi-
tions showed signicant differences with respect to how powders
were plasticised by water. Although permeate powders were the
least hygroscopic of the powders examined, the effect of moisture
content as a depressant of Tg increased in the order: whey perme-
81
100
80
60
Tgr , C
o
40
20
100
0
2 4 6 8 10
Moisture content, %
Fig. 6. Effect of moisture content on Tgr of non-fat spray dried powders as
determined by Method 2. Whey permeate (h), SMP (s), micellar casein (4).
ate > SMP > micellar casein. Such an effect reects the greater
water-induced molecular mobility of amorphous lactose (low
molecular weight) compared to the higher molecular weight milk
proteins, which are less able to undergo cooperative segmental
motion.
3.6. Tgr and powder functionality
The close correlation between the compression methods exam-
ined and Tge may be useful with regard to an appreciation of the
functionality of the powders tested. In dairy powders, potentially
deteriorative structural phenomena such as sticking, caking and
crystallisation occur at some temperature above Tg i.e. T  Tg
(Hogan et al., 2009). In fact, Le Meste et al. (2002) reported that
such events are never observed in the temperature/water content
domain below glass transition. Roos and Karel (1991) showed that
the sticking point of sucrosefructose mixtures was close to Tge and
about 20 C above Tgo. Because state transitions in amorphous
materials are dependent on their dynamic properties and are lar-
gely viscosity driven, it is possible that Tgr determined by Method
2 (equivalent to Tg endset temperatures) represents a more useful
reference temperature than Tgo or Tgm temperatures for predicting
the stability of dairy powders i.e. material viscosity associated with
Tgr is closer to the viscosities at which deteriorative, structural
changes in powders begin to occur.
The rates at which the surface viscosity of powders responds to
water or thermal plasticisation is likely to contribute to powder
stability. Bengoechea et al. (2007) reported that the difference be-
tween melt ow temperature and Tg of food proteins can be related
to the length of state transitions determined by DSC and DMTA. It
is also likely that the temperatures at which thermodynamically-
induced structural changes occur, such as sticking and crystallisa-
tion, is related to the nature (breadth/amplitude) of the transition
i.e. that the kinetics of state transitions are also related to post-
transitional change. Caution is required when comparing Tg values
in the literature as Tg is sometimes used to refer arbitrarily to dif-
ferent points in a transition, e.g. Tgo, Tgm or Tge, and the precise def-
inition is not always specied.
3.7. Differences in accuracy of control and measurement
A number of authors have suggested that determination of glass
transition in food materials by mechanical tests may be more
sensitive than thermal analysis (Kalivchesky et al. 1993; Boonyai
82 S.A. Hogan et al. / Journal of Food Engineering 99 (2010) 7682
and Bhandari, 2006; Rahman, 2006; Boonyai et al., 2007). Rahman
(2006) and Kasapsis et al. (2003) reported that calorimetric transi-
tions (determined by DSC) should not be considered as fully equiv-
alent with rheological transitions (determined by DMTA). In these
types of methods, samples are submitted to different physical
stresses (heating rates, temperature versus shearing or compres-
sion), experimental times and measurement frequencies, all of
which may cause the values of Tg to differ for the same material
(Gunasekaran and Mehmet Ak, 2000). Kasapsis et al. (2003) stated
that there was no clear-cut relationship between molecular mobil-
ity and thermal events in calorimetric experiments. Evidence from
this study, however, suggests that the acceleration in molecular
movement around Tgr may be equivalent to the end of thermal
glass transition (Tge). The same authors also suggested that a differ-
ent coupling of the imposed perturbations with the structural units
(with particular relaxation times) may be responsible for differ-
ences in the data obtained for these methods, although the funda-
mental reasons for such differences remain unclear (Rahman,
2006).
4. Conclusion
Effective techniques to determine the glassrubber transitions
of a range of both non-fat and fat-containing dairy powders were
developed using standard rheological equipment. Tgr values were
very closely correlated with Tge determined by DSC. Of the meth-
ods developed, Method 2, which measures Tgr as a function of
changes in normal force, was in better agreement with DSC data
than Method 1, which measures Tgr as a function of gap distance.
The techniques are suitable for use on powders with broad or
indistinct transitions, such as high protein powders, which can
be difcult to measure by DSC. In this way, the rheological meth-
ods developed in this study provide the means by which the glass
transition region can be identied thereby allowing complemen-
tary analysis by DSC. The techniques are also applicable to fat-con-
taining dairy powders, whose transitions may not be determined
by DSC, where powder moisture content results in an overlap of
glass transition and fat melting endotherms.
The methods allow accurate, rapid and repeatable methods of
analysis for glassrubber transitions in dairy powders and broaden
the range of application of laboratory rheometers in determining
the material behaviour of foods.
Acknowledgements
Funding was provided under the National Development Plan,
through the Food Institutional Research Measures (FIRM), adminis-
tered by the Irish Department of Agriculture and Food.
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