Journal of Cereal Science 31 (2000) 241–252

doi:10.1006/jcrs.2000.0308, available online at http://www.idealibrary.com on

Contribution of Major Ingredients during Baking of

Biscuit Dough Systems
S. Chevallier∗†, P. Colonna∗, G. Della Valle∗, D. Lourdin∗

∗ Institut National de la Recherche Agronomique, BP 71627, 44316 Nantes cedex 3, France;

† Danone, Centre de Recherches Jean Thèves, BP 16, 91207 Athis-Mons cedex, France

Received 20 September 1998

ABSTRACT
Nineteen dough systems were made of a combination of two to nine of the following ingredients:
flour, water, fats (coconut and/or palm oils), sugars (sucrose, invert) and chemical leaveners (ammonium
bicarbonate, sodium bicarbonate, citric acid and sodium acid pyrophosphate). Their thermal behaviour
was studied over a large temperature scale (20 °C to 160 °C). Thermal analysis of baking by three
different methods (DSC, DMTA and TGA) at the same heating rate (3 °C/min) provided information
about phase transitions, volume and mass changes of doughs during heating. Temperature ranges
over which all ingredients reacted were identified. Melting transitions of fats occurred between 10 °C
and 50 °C. Sugars increase temperatures of starch transitions. Chemical leaveners decrease rise
temperature, whereas fats and sugars have a delaying effect on their action. The texture of biscuits
results from interactions between ingredients; complete dough cannot thus be considered as merely
a simple addition of all components.

Keywords: baking, biscuit dough, physicochemical transformations, carbohydrates, DSC, DMTA,

TGA.

INTRODUCTION differential scanning calorimetry (DSC) in excess

Short doughs are characterised by their com-
position based upon three major ingredients: flour,
sugar and fat. Biochemical and physicochemical
reactions occurring in a biscuit dough during the
baking stage are very complex: water evaporation,
protein denaturation, starch destruction, browning
and Maillard reactions, dough expansion by pro-
duction and thermal expansion of gas. Many stud-
ies have been carried out on the starch destruction,
which is the main component of the dough, over
a large range of water contents1–3. Other studies
deal with the influence of ingredients or other
flour components on the gelatinisation of starch4–7.
In most cases, these studies are performed by
 : DMTA: dynamic mechanical ther-
mal analysis; DSC: differential scanning calorimetry;
TGA: thermogravimetric analysis.
Corresponding author: P. Colonna
water or with water to starch ratios above 0.6 (wet
basis, w.b.). Few results have been published on
the influence of ingredients at water contents below
0.6 (w.b.). Biscuit dough is representative of those
complex systems containing low amounts of water.
In the present study, a short dough has been
chosen as a reference to study its thermal be-
haviour. Our objective was to deconvolute the
complex DSC thermogram of this biscuit dough
by comparing the thermogram of a basic dough
made of flour and water to those obtained by
adding ingredients one-by-one into this basic
dough. Over a large temperature scale (20 °C to
160 °C), changes are related to the different ther-
mal events quoted above. Identification of the
influence of each ingredient might then be at-
tributed to the timing and extent of these events.
DSC has been chosen since it has been previously
extensively used to measure the thermal behaviour
of food systems. It has been reinforced by dynamic

0733–5210/00/050241+12 $35.00/0
242 S. Chevallier et al.
mechanical thermal analysis (DMTA) and thermo-
gravimetric analysis (TGA) to assess volume and
mass changes respectively over the same range of
temperature used in DSC.
EXPERIMENTAL
Materials
All ingredients were provided by LU (La Haye-
Fouassière, France). Wheat flour (moisture 14·8%
w.b., total protein 8·8% dry basis, d.b.), coconut
and palm oils were stored at 4 °C. Sucrose (two
grades: granulated and icing crystalline white suc-
rose) and chemical leaveners (ammonium bi-
carbonate (BCA), sodium bicarbonate (BCS), citric
acid and sodium acid pyrophosphate (SAPP)) were
stored at room temperature. Syrup was prepared
with water and granulated crystalline sugar (53 :
100 w/w) at 60 °C to facilitate sugar dissolution
and then stored at 4 °C. Invert sugar was a medium
invert containing 33% of sucrose and 37% of
water (d.b.).
Sample preparation
Flour was hydrated (35% w.b.) by mixing flour
and water. This level of water was chosen in order
to produce doughs that could be sheeted without
sticking or crumbling. Nineteen model doughs
were mixed in a Morton mixer (Motherwell, Scot-
land) at 24 °C in an all-in mixing procedure, then
sheeted and laminated in a sheeter fitted with two
rolling-mills (R-Tech, Wigan, U.K.). Basic dough
(No. 1) is a mixture of water and hydrated flour
(26·4 :100 w/w). Other dough systems (No. 2 to
No. 18) were obtained by adding ingredients to
the basic dough according to the recipes listed in
Table I. In order to assess the influence of each
ingredient, the ratio water-to-basic dough has been
maintained constant in all recipes. Therefore,
when added sugars contained water, the amount
of water added in the recipe was decreased with
respect to the amount of water contained in these
ingredients. Biscuit dough (No. 19) differed from
the dough containing all the ingredients (No. 18)
with respect to its water content which is lower
and closer to the water content of commercial
biscuit dough. After mixing the ingredients for
5 min, the dough was rolled in order to obtain a
2 m thick sheet. For DMTA experiments, pellets
(17 m diameter and 2 m height) were punched
out the dough sheet.
Methods
A DMTA Mk III (Rheometric Scientific, Lough-
borough, U.K.) was used in the compression mode
at a frequency of 5 Hz with a deformation amp-
litude of 10 lm. Assuming that the static force
applied (0.045N) to the sample in order to keep
contact with the plates can be neglected, the
change in the sample thickness (Dh) was also
recorded as a function of temperature. The rise is
defined as the ratio of the change in thickness to
the initial thickness (h0) (Dh/h0) with h0=2 m.
The weight loss of samples (30 mg) was measured
as a function of temperature on a thermo-
gravimetric analyser TGA7 (Perkin Elmer, Nor-
walk, CT, U.S.A.). From these results, a weight
loss rate was calculated.
DSC experiments on doughs were performed
on a DSC 121 (SETARAM, Caluire, France),
using 170 mg samples sealed in stainless steel pans.
The reference cell contained 105 mg of aluminium.
Temperature and enthalpy calibrations were car-
ried out with indium.
Runs were carried out in duplicate from 20 to
160 °C at the same heating rate of 3 °C/min for
all three types of experiment and average values
are reported.
RESULTS AND DISCUSSION
Typical data recorded from the three methods are
shown in Figure 1 with notations and temperatures
used to characterise the transitions observed on
basic dough. Because of the complexity of DSC
thermograms, transitions were characterised by
the temperature at the maximum of each event
rather than their enthalpy change. Every in-
dividual thermal transition of the DSC curve of
the dough with all ingredients (No. 18) is indicated
in Figure 2. Each homologous thermal event of
the basic dough is given the same number, which
is why the numbering begins at event 4 for basic
dough. For all doughs except dough No. 11, the
change in thickness of samples Dh was positive,
meaning that samples expanded. For dough No.
11, Dh was negative, meaning that the sample
collapsed during baking, this particular behaviour
is reported in Table III and discussed later.
Basic dough thermograms
DSC
The thermogram of basic dough (No. 1) exhibited
three major endotherms (Figure 1). The first,
 Contribution of major ingredients during baking of biscuit dough systems 243

Table I Dough recipes—the content of each ingredient is given in parts by weight

No. Model Hydrated Water Chemical

systems flour Sugars Fat leaveners

Icing Invert Syrup Coconut Palm mixa BCA

1 basic dough 100 26·4 — — — — — — —

2 +icing sugar 100 26·4 11·2 — — — — — —
3 +invert sugar 100 24·0 — 7·3 — — — — —
4 +syrup 100 18·9 — — 26·9 — — — —
5 +icing-invert sugars 100 24·0 11·2 7·3 — — — — —
6 +icing sugar-syrup 100 18·9 11·2 — 26·9 — — — —
7 +invert sugar-syrup 100 16·5 — 7·3 26·9 — — — —
8 +3 sugars 100 16·5 11·2 7·3 26·9 — — — —
9 +coconut 100 26·4 — — — 9·3 — — —
10 +palm 100 26·4 — — — — 6·2 — —
11 +fat 100 26·4 — — — 9·3 6·2 — —
12 +mixa 100 26·4 — — — — — 0·9 —
13 +BCA 100 26·4 — — — — — — 1·3
14 +leaveners 100 26·4 — — — — — 0·9 1·3
15 +fat-leaveners 100 26·4 — — — 9·3 6·2 0·9 1·3
16 +fat-sugars 100 16·5 11·2 7·3 26·9 9·3 6·2 — —
17 +sugars-leaveners 100 16·5 11·2 7·3 26·9 — — 0·9 1·3
18 +all ingredients 100 16·5 11·2 7·3 26·9 9·3 6·2 0·9 1·3
19 biscuit dough 100 0·0 11·2 7·3 26·9 9·3 6·2 0·9 1·3

mixa: BCS/citric acid/SAPP: 0·6/0·1/0·2.

numbered 4 with a minimum at 70 °C, a large
one (endotherm 5) at 101 °C and a third one
(endotherm 6) at 122 °C (Table II).
These events can be related to thermal events
observed when studying thermal transitions of
starch at intermediate water contents (lower than
60% w.b.). DSC scans of wheat starch-water mix-
ture (1 : 1) exhibit three endotherms1,3. The first
(around 60 °C, depending upon the author) has
been assigned to a co-operative, water-mediated
melting of starch crystallites, the second (around
90 °C) to the melting of remaining crystallites2,8,9,
while the third (around 110 °C) has been shown
to be due to a melting transition of the amylose-
lipid complex1,10,11. As the water level is pro-
gressively reduced, the intensity of the first en-
dotherm is reduced but the endotherm remains
at the same temperature. The second and third
endotherms move to higher temperatures but at
different rates, so that at water contents lower
than 30%, both endotherms merge into a single
endotherm above 120 °C. In the present study,
the water content was 36·8% (w.b.), which gives
a three-endotherm DSC scan. Published tem-
perature ranges that characterise these endotherms
for wheat starch-water systems1,3,12, are just below
the values measured with basic dough: (53 °C,
66 °C) for thermal transition 4, (86 °C, 96 °C)
for thermal transition 5 and (170 °C, 125 °C) for
thermal transition 6 at an equivalent water content.
The higher transition temperatures observed here
with the basic dough sample cannot be explained
by differences in heating rates used in these ex-
periments; they could be due either to the lower
damaged starch levels in biscuit flours, which are
milled from soft wheats, or to the presence of
other components of flour such as arabinoxylans13,
hydrophilic compounds affecting the availability
of water, or gluten. Other studies5 on a wheat
flour-water system with a water content of 50%
(w.b.) reported thermal transitions 4, 5 and 6 with
minima, respectively, at 62 °C, 82 °C and 110 °C.
The amylopectin crystallite melting temperature
of 70 °C found in the present study is 8 °C higher,
while the other two temperatures are also higher
because of the lower water content.
DMTA and TGA
DMTA was used to determine changes in sample
thickness (rise or collapse) as a function of tem-
perature. A typical trace is shown in Figure 1.
Samples of basic dough were among samples that
had the greatest rise: 152% (Dh/h0). The tem-
perature range corresponding to this event
244 S. Chevallier et al.

DSC

1 mW
exo
heat flow

4
No. 1
6

5
T max

TGA No. 1
weight loss rate

20 µg/s

T onset

T max

DMTA 50%
rise ∆h/ho

No. 1

T onset

No. 1
E' (log scale)

0 20 40 60 80 100 120 140 160 180

Temperature (°C)

Figure 1 Typical plots from DSC, TGA and DMTA illustrating the different temperatures chosen to characterise phase
transitions for basic dough (No. 1).

(132 °C, 144 °C) and that corresponding to weight corporated into the dough during mixing and
loss obtained from TGA, (135 °C, 151 °C) over- steam formed by evaporation of dough water are
lapped. the two causes of the rise that occurred in the
Expansion, in the DMTA oven, of air in- basic dough.
 Contribution of major ingredients during baking of biscuit dough systems 245

to storage and dough mixing conditions. Therefore

1 mW comparison of thermal transitions between ther-
No. 1
mograms is not straightforward.
Endothermic heat flow

No. 8
DSC
Thermograms of doughs containing fats (No. 9 to
No. 11) exhibited a series of thermal transitions
No. 11
numbered from 0 to 2 and 4 to 6. Characteristic
temperatures of the various thermal transitions
are reported in Table II. Dough No. 9 is char-
acterised by five thermal transitions: transitions 0
3
2 6 No. 18 and 1 whose maxima are located at 23 °C and
1 36 °C, respectively, and transitions 4, 5 and 6
4 5 whose maxima are at 71 °C, 101 °C and 123 °C,
0
respectively. These results can be compared with
0 20 40 60 80 100 120 140 160 thermal events observed for basic dough. Thermal
Temperature (°C) transitions 4, 5 and 6 can be attributed to starch
melting, while transitions 0 and 1 result from
Figure 2 Typical DSC thermograms. No. 1: basic dough, thermal transitions of coconut oil used in dough
No. 8: basic dough+sugars, No. 11: basic dough+fats, No.
18: basic dough+all ingredients. No. 9.
Dough No. 10 also reveals the same pattern. As
preceedingly, transitions 1 and 2, whose minima
are at 41 °C and 52 °C, respectively, may be
Contribution of lipids
attributed to thermal transitions of palm oil,
Natural fats are composed of mixtures of numerous whereas transitions 4, 5 and 6 with minima at
triglycerides. They frequently exhibit complex 70 °C, 99 °C and 122 °C, respectively, can be
temperature-dependent properties in relation, on attributed to starch transitions.
one hand, to fat composition and the behaviour Finally, dough No. 11 exhibits six thermal trans-
of specific triglycerides14 and, on the other hand, itions on DSC scans: transitions 0, 1 and 2 at 21 °C,

Table II Characteristic temperatures from DSC thermograms

No. Model systems Tmax (°C) thermal transitions

0 1 2 3 4 5 6

1 basic dough — — — — 70 101 122

2 +icing sugar — — — — 78 106 125
3 +invert sugar — — — — 72 100 123
4 +syrup — — — — 84 104 125
5 +icing-invert — — — — 80 104 126
6 +icing-syrup — — — — 89 106 126
7 +invert-syrup — — — — 88 108 127
8 +3 sugars — — — — 95 113 129
9 +coconut 23 36 — — 71 101 123
10 +palm — 41 52 — 70 99 122
11 +fat 21 36 48 — 71 99 121
12 +mix — — — — 68 99 125
13 +BCA — — — — 68 100 126
14 +leaveners — — — — 70 100 125
15 +fat-leaveners 21 33 48 — 69 100 125
16 +fat-sugars 19 35 48 — 93 110 129
17 +sugars-leaveners — — — 73 96 113 131
18 +all ingredients 19 35 45 72 94 114 130
19 biscuit dough 19 37 48 69 — 111 129
246 S. Chevallier et al.
36 °C and 48 °C, respectively, and transitions 4,
5 and 6 at 71 °C, 99 °C and 121 °C, respectively.
As for doughs No. 9 and No. 10, these last three
events involve thermal transitions of starch. The
first transitions observed between 10 °C and 55 °C
(Table II) result from the thermal transitions of fats.
Transition 0 involves mainly thermal transitions of
coconut oil, which has a melting point15 of 26 °C.
Thermal transition 2 reflects those of palm oil with
melting temperatures range15 from 27 °C to 45 °C.
Thermal transition 1 cannot be attributed to one
or the other oil, but most likely results from thermal
transitions of both oils.
The use of DSC for the investigation of thermal
properties of fats gives numerous thermal trans-
itions16. These complex thermograms are not easily
interpretable: they depend on the whole thermal
history of the sample, including heating and cool-
ing rates17. In our series of experiments, although
the temperature-controlled mixer was set up at
24 °C, final mixing temperatures were 27·6 °C,
29·0 °C and 30·8 °C for doughs No. 9, No. 10
and No. 11, respectively. Therefore, these samples
have different thermal histories which may explain
slight discrepancies between temperatures of ther-
mal transitions. Moreover, as a function of con-
ditioning, several polymorphic crystalline species
(a, b′ or b) are observed for each pure tri-
glyceride14; mixtures of triglycerides may form
mixed crystals, whose structures are different from
those formed by pure compounds. In that case,
identification of the species, the domain of which
is delimited by each DSC melting or crystallisation
peak, is rather complex and often quite impossible
without the help of techniques that yield structural
information (e.g. X-ray diffraction, infrared spec-
troscopy, etc.). These techniques cannot be carried
out on dough related samples due to their complex
chemical composition.
DMTA and TGA
The main features of those thermograms are re-
ported in Table III. A sample of dough No. 10
has a large rise (Dh/h0): 139% vs. 32% for dough
No. 9. This difference may be explained by the
difference in melting temperatures of these two
kinds of oils. Studies on the role of fat in the
stabilisation of gas cells in cake batters and in
bread doughs have emphasised the importance of
the adsorption of a number of fat crystals at the
surface of gas bubbles in dough18,19. The proposed
mechanism is that when crystals melt during bak-
ing, the fat–liquid interface of the adsorbed crystals
provides a source of extra interfacial material
for the bubble surface, which allows expansion
without rupture of the bubble. In that case, doughs
with palm oil, which has a higher melting point
than coconut oil, should rise more during baking.
In samples of dough No. 9, all crystals melt at the
beginning of baking, even during mixing, to form
droplets, and no crystals are available afterwards
for adsorption to bubbles.
Samples from dough No. 11 behaved totally
differently from others samples. During the initial
stages of heating, the sample spread under the
plate between 42 °C and 95 °C. In this temperature
range, the collapse of the structure was 41% of
the initial height; then in a later stage, the dough
rose 5% from 124 °C to 137 °C, leading to a final
collapse of 36%. The rise in the second stage can
be attributed to water evaporation since it happens
over the same temperature range (130 °C, 146 °C)
as the weight loss identified by TGA. An ex-
planation of the different behaviour of dough No.
11 is that there would be a critical fat content
over which mechanical properties of doughs would
be drastically modified: samples would flow with
increasing temperatures, suggesting that dough
behaves like a suspension of flour particles, held
by a continuous fat phase.
Contribution of sugars
DSC
Like the thermogram of basic dough, thermograms
of doughs containing sugars (doughs No. 2 to No.
8) exhibited three major endotherms numbered
4 to 6 (Table II). They were shifted to higher
temperatures as the sugar content of doughs in-
creased. Thermal transition 4 had a minimum of
70 °C for basic dough, 72 °C for dough No. 3,
78 °C for dough No. 2, 80 °C for dough No. 5,
84 °C for dough No. 4, 88 °C for dough No. 7,
89 °C for dough No. 6 and 95 °C for dough
No. 8. The influence of sugar addition was less
pronounced for thermal transitions 5 and 6, the
temperatures of which remained in the ranges
(100–113 °C) and (123–129 °C), respectively. The
temperature of the melting endotherm (transition
4) was directly proportional to the quantity of
sugars added to the dough [Fig. 3(a)], and also to
the amount of water expressed in parts by weight
of dry hydrophilic compounds, i.e. all ingredients
except fats [Fig. 3(b)].
Various techniques such as optical microscopy20,
 Contribution of major ingredients during baking of biscuit dough systems 247

Table III Characteristic temperatures from TGA and DMTA thermograms

TGA DMTA-plate displacement DMTA

No. Model systems step 1 step 2 E′

(105 Pa)
Tonset Tmax Tonset Tmax Dh/h0 Tonset Tmax Dh/h0 at Tonset
(°C) (°C) (°C) (°C) (%) (°C) (°C) (%) rise

1 basic dough 135 151 — — — 132 144 152 0·4

2 +icing sugar no run — — — 136 148 130 0·7
3 +invert sugar no run — — — 136 148 130 0·5
4 +syrup no run — — — 124 149 57 2·0
5 +icing-invert no run — — — 137 154 77 0·8
6 +icing-syrup no run — — — 119 148 56 1·0
7 +invert-syrup no run — — — 115 149 63 1·3
8 +3 sugars 124 151 — — — 124 143 56 1·0
9 +coconut no run — — — 131 146 32 1·6
10 +palm no run — — — 140 153 139 0·2
11 +fat 130 146 42 95 41 124 137 5 —
collapse
12 +mix 142 161 49 107 40 120 144 105 1·2
13 +BCA 136 155 49 84 32 102 122 131 1·3
14 +leaveners 146 152 48 78 34 93 115 195 0·8
15 +fat-leaveners 74 130 — — — 89 114 73 1·5
16 +fat-sugars 99 123 no data—impossible to laminate dough
17 +sugars—leaveners 69 114 — — — 88 109 73 1·5
18 +all ingredients 84 117 no data—impossible to laminate dough
19 biscuit dough 76 103 — — — 76 110 27 1·4

rheometry21, differential scanning calorimetry2 and
electron spin resonance22 have been used to study
the influence of sugars on starch gelatinisation and
melting. The general trend is for an increase in
gelatinisation temperature to occur, sugar content
increases, but the exact effect depends on the
nature of the sugar. Systems of lower water content
(10% w.b.) and higher sucrose content (30% w.b.)
which correspond to cookie doughs, have been
studied by DSC4,7. In those systems, when sugar
content increases, an increase in gelatinisation
temperature is observed together with a decrease
in gelatinisation temperature. Two systems, water-
flour and water-sucrose-flour (ratio sucrose : flour
1 : 5 d.b.) at the same weight fraction of water (40%
w.b.) were studied here by DSC. Thermograms are
presented in Figure 4. Both exhibit three thermal
transitions (4, 5 and 6) at 68 °C, 88 °C and 111 °C
for the water-flour system and at 78 °C, 93 °C and
115 °C for the water-sucrose-flour system. Those
transitions may be attributed to starch melting
as stated earlier, but the increases in transition
temperature cannot be attributed solely to the
decrease in water content, since in these ex-
periments, the water fraction was the same in both
systems. These results confirm that, in our lower
moisture systems, sucrose increases the thermal
transition temperatures. In the literature, two hy-
potheses have been proposed for explaining this
effect: (a) the activity of sugar(s) to compete for
water with starch and thereby to reduce water
activity21,23,24, (b) sugar–starch interaction4,20,25.
Elucidation of the sucrose mechanism is outside
the scope of this work.
DMTA and TGA
The rise that occurred in doughs No. 2, No. 3
and No. 5 began at 136 °C (Table III). Those
doughs contained sugars but no syrup. However,
the extent of rise for those doughs decreased as
the sugar content increased: 170% for dough No.
3, 130% for dough No. 2 and 77% for dough No.
5. Doughs containing syrup began to rise at lower
temperatures (between 115 °C and 124 °C) and to
a smaller extent (57% for dough No. 4, 63% for
dough No. 7 and 56% for doughs No. 6 and No.
8). The acceleration in weight loss determined by
TGA and the rise of dough No. 8 both started at
124 °C.
The rise of dough No. 8 can be linked to weight
loss, i.e. to the evaporation of water. Doughs with
added sugars tended to rise less and starting at
248 S. Chevallier et al.

(a)
100
water/dry flour
40/60 0.5 mW

Endothermic heat flow

90
Temperature (°C)

4
80 6
water/dry sucrose/dry flour
40/10/50
5
70 6

4
60 5
0 10 20 30 40
Dry sugar weight per 100 g of basic dough

20 40 60 80 100 120 140

(b)
120 Temperature (°C)
Temperature (°C) of event (4) DSC

Figure 4 DSC thermograms of flour and sucrose-flour

110 (1 : 5 d.b.) both at a water content of 40% (w.b.).

100

90 Contribution of chemical leaveners

80
70
60
20 30
Water content per 100 g of dry hydrophilic compounds
Figure 3 Starch melting temperature (thermal transition 4)
from DSC thermograms as a function of sugar and water
contents. Top curve (a): doughs containing sugars (No. 2 to
No. 8 and No. 16 to No. 18), bottom curve (b): all doughs.
lower temperatures than the basic dough. Dough
No. 7 containing sugars in liquid form (invert
sugar and syrup) had began to rise at the lowest
temperature of 115 °C, while samples with no
syrup began to rise at 136 °C. Sugars in liquid
form may distribute in the dough during mixing
and laminating, whereas crystalline sugar (sucrose)
may remain crystalline in view of the fact that its
melting temperature is 185 °C, facilitating greater
water availability for binding to flour particles.
During the heating stage, water bound to sugars
may evaporate and be released more easily, hence
at a lower temperature than water bound to flour.
DSC
Thermograms of doughs (No. 12 to No. 14) con-
taining chemical leaveners exhibited three thermal
transitions numbered 4, 5 and 6 (Table II), with
minima temperatures of 68 °C, 99 °C and 125 °C
40 50 60
for dough containing the mix (No. 12), 68 °C,
100 °C and 126 °C for dough containing BCA
(No. 13), 70 °C, 100 °C and 125 °C for dough
No. 14 (i.e. mix and BCA). For a given thermal
transition (4, 5 or 6), the transition temperatures for
the various doughs were not significantly different
from one another and they corresponded to the
temperatures determined for the basic dough ther-
mogram; 70 °C, 101 °C and 122 °C for transitions
4, 5 and 6, respectively. The thermal transitions
observed in this series of experiments may be
attributed to thermal transitions of starch. No
DSC detectable transitions attributable to chem-
ical leaveners could be found for doughs No. 12
to No. 14. DSC scans of chemical leaveners alone
exhibited an endotherm with a maximum at 63 °C
for citric acid alone and 119 °C for BCA alone.
DSC scans for the mixture exhibited two en-
dotherms with minima at 69 °C and 99 °C (data
not shown). Those endotherms reflected thermal
decomposition of the chemical leaveners. There-
fore, such reactions might contribute to thermal
transitions 4 and 5. Those thermal transitions
occurred at the same temperatures as the thermal
transitions of starch: the associated endotherms
 Contribution of major ingredients during baking of biscuit dough systems
overlap on DSC thermograms. However, the con-
tribution of chemical leaveners to the transitions
observed in DSC thermograms is very small, since
the amount of the chemical leaveners present in
dough is small compared with the amount to starch
(3·7 : 100 d.b).
DMTA and TGA
DMTA results (Table III) for doughs containing
chemical leaveners showed that those doughs be-
haved differently: the rise shown by samples (No.
12 to No. 14) began as early as 48 °C and occurred
in two stages. The rise for dough No. 14 began at
48 °C and continued until 115 °C in two stages,
stage 1 (34%) followed by stage 2 (195%). Dough
No. 14 showed the most substantial rise: 229%
(total sum of the two rise stages), while those of
doughs No. 12 and No. 13 were 145% and 162%
respectively. No significant weight loss was de-
tected by TGA over the temperature range of
stages 1 and 2, since chemical leaveners represent
at most 1·7% of the total weight of samples (data
not shown).
The weight loss that occurred above 136 °C for
doughs with chemical leaveners was consequently
due to water evaporation, which does not con-
tribute to the rise in such doughs in contrast to
doughs with no chemical leaveners, i.e. No. 1 and
No. 8. The role of chemical leaveners is to induce
an early rise during the baking stage. Rise tem-
peratures cannot be directly compared with ther-
mal transitions detected in DSC experiments, since
operating conditions are different (DSC pans are
hermetically sealed and internal pressure increases
with temperature), but it can be assumed that the
mix would contribute more to stage 1 (40% over
(49–107 °C) for dough No. 12 vs. 32% over
(49–84 °C) for dough No. 13) and BCA would
contribute more to stage 2 (131% over
(102–122 °C) for dough No. 13 vs. 105% over
(120–144 °C) for dough No. 12). Those tem-
perature ranges can be related to the thermal
transition temperatures determined by DSC (63 °C
for acid citric contained in the mix and 119 °C
for BCA).
Combination of ingredients
In this part of the study, the objective was to
determine how each of the three types of ingredient
interact with the others. From DSC scans of ter-
tiary systems—one ingredient, water, flour—two
249
domains can be considered: (a) transition 0 to 2
characterising lipids transitions and (b) transitions
4 to 6 characterising starch transitions influenced
by sugars and possibly chemical leaveners.
Lipids interactions
DSC thermograms of doughs with fats all exhibited
three thermal transitions numbered 0 to 2 between
10 °C and 55 °C. Their minima were located at
21 °C, 33 °C and 48 °C for dough No. 15, 19 °C,
35 °C and 48 °C for dough No. 16, 19 °C, 35 °C
and 45 °C for dough No. 18 and 19 °C, 37 °C and
48 °C for dough No. 19 (Table II).
Thermal transitions 0 to 2 occurred at similar
temperatures for any recipe including fat. In other
words, there was no influence of the other in-
gredients on the thermal transitions of fats de-
tectable by DSC: this is an additive system.
Sugars interactions
DSC thermograms of doughs with sugars exhibited
thermal transitions 4, 5 and 6 located at 93 °C,
110 °C and 129 °C for dough No. 16, 96 °C,
113 °C and 131 °C for dough No. 17 and 94 °C,
114 °C and 130 °C for dough No. 18 (Table II).
Comparison of these values with those for dough
No. 8 (basic dough with sugars) showed that there
was no interaction between ingredients as far as
thermal transitions determined by DSC were con-
cerned. But, as stated before, sugars interact with
starch and have a delaying effect on its thermal
transitions. Table IV presents the mean and stand-
ard deviation values for temperatures char-
acterising the thermal transitions of starch
(transitions 4, 5 and 6) with sugars: 94 °C, 112 °C
and 130 °C, or without sugars: 70 °C, 100 °C and
124 °C, with a maximum standard deviation of 2.
Characteristic temperatures for these transitions
were significantly higher for doughs containing
sugars. Each sugar played a role governed by its
concentration rather than its initial physical state.
Chemical leavener interactions
DSC thermograms of dough with chemical lea-
veners and fats (No. 15) exhibited thermal trans-
itions numbered 4, 5 and 6 at 69 °C, 100 °C and
125 °C (Table II). Those transitions corresponded
to those identified for basic dough, i.e. to thermal
transitions of starch. But DSC thermograms for
doughs with chemical leaveners and sugars ex-
hibited 4 thermal transitions numbered 3 to 6
250 S. Chevallier et al.

Table IV Mean (l) and standard deviation (r) values for thermal transition 4, 5 and 6 with regard to sugar content

Model systems Tmax (°C) for thermal transitions

4 5 6

l r l r l r

all doughs No. 1 to No. 19 79 11 105 5 126 3

with no sugar No. 1, No. 9 to No. 15 70 1 100 1 124 2
with different sugars No. 2 to No. 8, No. 16 to No. 18 87 8 108 5 127 3
with all three sugar types No. 8, No. 16 to No. 18 94 1 112 2 130 1

(Figure 2) at 73 °C, 96 °C, 113 °C and 131 °C 140

respectively for dough No. 11, and at 72 °C, 94 °C, No. 1

Rise temperature (°C)

114 °C and 130 °C for dough No. 18. Thermal 120 dough
transitions 4, 5 and 6 appear at the same tem- with fats doughs with
except No.1
peratures for dough No. 8 (basic dough with sug- 100 sugars
ars), respectively, 95 °C, 113 °C and 129 °C. Those No. 15 No. 17
transitions have been identified as thermal trans- 80 No. 18
No. 19
doughs
itions of starch influenced by sugars. Therefore with
thermal transition 3 at 73 °C and 72 °C for doughs 60 leaveners

No. 17 and No. 18, respectively, may be due to

chemical leaveners.
This contribution was not detected for the other
doughs since it merged into the endotherm for
starch melting. The thermogram for dough No.
19 also exhibited thermal transition 3 at 69 °C but
did not exhibit thermal transition 4. Because of
the lower water content, this transition was shifted
to higher temperatures and merged into thermal
transition 5 (starch melting). When considering all
the doughs containing chemical leaveners, it can
be concluded that no interaction between chemical
leaveners and the other ingredients was detectable
by DSC.
Since some doughs were impossible to laminate
(No. 16 and No. 18), no data are available for the
rise of these samples. Therefore, DMTA ther-
mograms yield information only on the inter-
actions of the chemical leaveners with the other
ingredients. The rise of samples of doughs No.
15 and No. 17 occurred at 89 °C and 88 °C,
respectively, and reached 73% for both samples
at the end of baking, whereas samples containing
only leaveners showed two rising stages (Table
III). Consequently, interactions between chemical
leaveners and the other ingredients (fats, sugars)
were detectable by combined DMTA and TGA
on a macroscopic scale, while no interaction was
detected with regards to transitions detected by
DSC. Therefore, the dough rise for samples con-
taining chemical leaveners and either fats or sugars
40
60 70 80 90 100 110 120
Maximum temperature (°C) of
starch melting (event 4)
Figure 5 Rise temperature versus melting temperature for
different doughs. Β composite doughs: No. 1 basic dough,
No. 15 basic dough+fats and leaveners, No. 17 basic
dough+sugars and leaveners, No. 18 basic dough+all in-
gredients, No. 19 biscuit dough, Χ: doughs with fats, Μ:
doughs with sugars, Ε: doughs with leaveners.
occurred at a temperature intermediate between
the dough rise temperature for basic dough
(132 °C) and those for doughs containing chemical
leaveners (No. 12 to No. 14), 48 °C. Adding either
fats or sugars delayed the action of chemical lea-
veners, which occurred concomitantly with the
weight loss due to water vaporisation observed by
TGA. These results are in agreement with reports
of works on related products. Sugar depressed the
rate at which gas was given off due to chemical
leaveners by 5 to 10% depending upon sugar
content26. Fats delay the release of carbon dioxide
during baking of bread dough27.
By plotting the dough rise temperature against
temperature of thermal transition 4 for all doughs,
an overview of the different transitions was ob-
tained and the role of each ingredient could be
identified (Figure 5). Major trends were the de-
crease in dough rise temperature caused by chem-
 Contribution of major ingredients during baking of biscuit dough systems
200
%(∆h/h0) = 197.5
exp(–8.9.10–6 E' )
doughs with
leaveners R2 = 0.84
150 No. 1
Rise ∆h/h0 (%)
100
No. 15
No. 17
50
No. 19
0 0.5 × 105 1.0 × 105 1.5 × 105 2.0 × 105 2.5 × 105
E' (Pa)
Figure 6 Rise (Dh/h0) versus E′ modulus at the beginning
of dough rise (Tonset of step 1 or step 2 in DMTA results of
Table III) for different doughs. Β composite doughs: No. 1
basic dough, No. 15 basic dough+fats and leaveners, No.
17 basic dough+sugars and leaveners, No. 19 biscuit dough,
Χ: doughs with fats, Μ: doughs with sugars, Ε: doughs with
leaveners.
ical leaveners and the increase in thermal transition
4 temperature caused by sugars resulting in a
combined influence for doughs No. 17, No. 18
and No. 19.
CONCLUSION
Thermal analysis of baking by three different
methods (DSC, DMTA, TGA) at the same heating
rate of 3 °C/min provided informations about
thermal transitions of ingredients and volume and
mass changes. These measurements give an in-
dication of behaviour during baking, but are not
identical to baking.
Temperature ranges over which the different
ingredients react have been identified. Results
from DMTA and TGA enabled the contribution
of each ingredient towards dough rise to be de-
termined. Dough rise is governed by chemical
leaveners, but interactions between ingredients
have been highlighted. Fats and sugars had a
delaying effect on the action of the chemical lea-
veners. Since the texture of biscuits results from
strong interactions between ingredients, the system
cannot be considered as additive. For a better
understanding of the development of the biscuit
texture, the rises for all dough samples (except
dough No. 11) were plotted against the elastic
modulus, E′, recorded by DMTA (Figure 6). Vari-
ations in E′ over the complete temperature interval
of study (20 to 160 °C) was very difficult to interpret
251
because of the complicated modifications oc-
curring during the thermal treatment, in particular
bubble expansion. Therefore, values reported for
E′ correspond to the dough rise temperature for
the samples (Tonset of step 1 or step 2 in DMTA
results of Table III, Figure 1). For doughs with no
chemical leaveners (No. 1 to No. 10), the lower
the rise, the higher the elastic modulus. This
variation illustrates that thermomechanical prop-
erties of doughs, expressed here by an increase
in rigidity, which precludes expansion of dough
samples. Moreover, for a given value of the elastic
modulus, dough rise is greater for doughs with
chemical leaveners than doughs with sugars or fats.
For the same rigidity, gas produced by chemical
leaveners will therefore enhance expansion of
dough samples.
For the complex DSC thermogram of biscuit
dough, each thermal transition has been attributed
to an ingredient, the only interaction identified
with regard to phase transitions was the influence
of sugars on thermal transitions of starch. As far
as the other ingredients are concerned (fats and
chemical leaveners), the system could be con-
sidered as additive. Thermal transitions and vol-
ume and mass changes could be interpreted
altogether, which helps the understanding of phe-
nomena involved in baking. Fats, by their melting
phase transitions, may play a role in the sta-
bilisation of gas cells in doughs and influence the
rise during baking. Phase transitions of starch, even
though they have no straightforward influence
on dough rise, may influence the biscuit texture
through the state of cell walls. Moreover, DSC
thermogram of flour in reduced water content
(lower than 60% w.b.) remains very complex. The
roles of flour components, particularly starch and
protein need further studies.
Acknowledgements
The authors are indebted to C. Larue for her skillfull
technical assistance and B. Garnier (ISITEM) for the
use of the TGA facility.
 2000 INRA
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