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Author’s Accepted Manuscript

Understanding the structure of ganache: Link


between composition and texture

Aurelie Saglio, Julien Bourgeay, Romain Socrate,


Alexis Canette, Gerard Cuvelier

www.elsevier.com

PII: S1878-450X(17)30137-3
DOI: https://doi.org/10.1016/j.ijgfs.2018.05.003
Reference: IJGFS101
To appear in: International Journal of Gastronomy and Food Science
Received date: 3 November 2017
Revised date: 27 March 2018
Accepted date: 9 May 2018
Cite this article as: Aurelie Saglio, Julien Bourgeay, Romain Socrate, Alexis
Canette and Gerard Cuvelier, Understanding the structure of ganache: Link
between composition and texture, International Journal of Gastronomy and
Food Science, https://doi.org/10.1016/j.ijgfs.2018.05.003
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Understanding the structure of ganache: link between composition and texture

Aurelie Saglioa, Julien Bourgeaya, Romain Socratea, Alexis Canetteb,c, Gerard Cuvelierd
a
Valrhona SAS, 8 quai du general de Gaulle, 26600 Tain l’Hermitage, France
b
MICALIS Institute, INRA, AgroParisTech, Université Paris-Saclay, 78350 Jouy-en-Josas,
France
b
IBPS Institute, Sorbonne Université, CNRS, 75005 Paris, France
d
UMR GENIAL, AgroParisTech, INRA, Université Paris-Saclay, 1 avenue des Olympiades,
91300 Massy, France

aurelie.saglio@valrhona.fr

julien.bourgeay@valrhona.fr

romain.socrate@valrhona.fr

alexis.canette@sorbonne-universite.fr

gerard.cuvelier@agroparistech.fr

1
ABSTRACT

Ganache is a common chocolate preparation used as a filling for chocolate bonbons. The aim
of this study was to understand the links between ganache composition, microstructure and
macroscopic behaviour. The study proved that hot ganache is an oil-in-water emulsion, which
evolves upon cooling into a bicontinuous system. Dark and white model ganaches were
manufactured to understand the roles of components such as sugar, water, fat and cocoa in
ganache structure and texture. Water activity and consistency of hot ganache, as well as
firmness of crystallised ganache were measured. Real ganaches, standard and split (i.e.
destabilised), were also manufactured, and analysed by confocal laser scanning microscopy
(CLSM). Results showed that the main parameters explaining ganache behaviour and texture
were the quantity of free water in ganache, and the balance between the aqueous phase and
the fat phase. Results also highlighted the importance of non-fat cocoa in ganache, as a
texturing agent that can help stabilise (in the case of standard ganache) or destabilise ganache
(in the case of split ganache).

Keywords

ganache; chocolate; microstructure; emulsion; fat

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1. INTRODUCTION

Ganache is one of the most common chocolate preparations. It has been invented in France in
the 1850s, by accidentally pouring water over chocolate. Hence the name ganache, which
means in French “jowl”. Traditionally, ganache is a mix of chocolate and cream, that is
melting in the mouth (Robuchon, 2009). Ganache can be used as a glaze, as a filling for
pastries or for chocolate bonbons. There is no legislation about ganache, regarding
composition or manufacturing process. Therefore, there are as many recipes and processes for
ganache as there are pastry chefs. In addition to chocolate and cream, recipes can include
other texturing ingredients such as sugar or butter (Herrero and Etienne, 2009; Richard,
2014).

Very few scientific studies deal with ganache. Ganache main ingredients, chocolate and
cream, have complex microstructures. Chocolate is a suspension of sucrose, cocoa and milk
(for milk or white chocolate) particles in a fat phase (cocoa butter). Chocolate manufacture
ensures that cocoa, sucrose and milk particles have a size around 10 µm, so that they are not
perceived in the mouth (Auty et al., 2001). Cocoa butter has a short melting range: at 20°C, it
has a solid fat content between 70 % and 80 %, and at 37°C it is completely melted (Pontillon,
1998). Cocoa butter hardness depends on cocoa origin: for instance Indonesian cocoa butters
are harder than Brazilian cocoa butters (Beckett, 2017). For milk and white chocolate that
contain milk fat as well as cocoa butter, the melting range is lower. For example, white
chocolate containing 15 % milk fat in its fat phase has a solid fat content of 65 % at 20°C
(Pontillon, 1998). In addition, cocoa butter is a polymorphic fat (Loisel et al., 1998, Rousseau,
2007).

Cream is an oil-in-water emulsion (McGee, 2007). Milk fat is stabilised by proteins and
phospholipids (Bridier et al., 2015), forming fat globules that are very heat-resistant. In
homogenised cream, milk fat globules can have a size of 1 µm or less (Hayes and Kelly,
2003; Lopez et al., 2015). The water phase contains sugars (mainly lactose) and water-soluble
proteins. On the contrary, butter is a water-in-oil emulsion. Water droplets in butter are
stabilised by milk fat crystals. Indeed, milk fat has a wide melting range: from -40°C to 40°C
(Boutonnier, 2006).

Thus, ganache is a mix between an oil-in-water emulsion (cream), and a fat suspension
(chocolate). In a chocolate and cream mix, cream is often considered as an aqueous phase,
and chocolate a fat phase, so ganache is said to be an emulsion. According to McGee (2007),
when chocolate is mixed with cream, its sugars are dissolved in the water from the cream.
Cocoa particles do not dissolve but tend to absorb water. Ganache is therefore an oil-in-water
emulsion, and cocoa thickens the water phase. However, for Herrero and Etienne (2009)
ganache is a water-in-oil emulsion. For others like Farah (2017), cocoa particles could destroy
the emulsion when swelling. What ganache structure becomes after this step is not clear.
Others like This (2010) mention fat crystallisation but do not specify its influence on ganache
structure. As ganache is often cooled at room temperature, its cooling rate is quite slow:
around 0.5°C/min.

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Emulsion formation and stability have been widely studied, on model products as well as real
products that could be related to ganache. For instance, emulsions can be stabilised by
particles: these are Pickering emulsions (Dickinson, 2010). A large variety of particles can be
used for this purpose, from nanoparticles to colloidal particles, including clusters of
nanoparticles behaving as larger particles. Cocoa particles from chocolate have a mean size of
10 µm (Beckett, 2017) and do not entirely dissolve in water as they contain insoluble fibres
and starch (Pontillon, 1998). They could help stabilise a chocolate and cream emulsion by
migrating at the interfaces.

Emulsion crystallisation has also been studied (Cansell, 2005; Thivilliers, 2007), through
products such as ice cream or whipped cream (Drelon et al., 2006). Crystallisation of oil-in-
water emulsions can destroy the emulsion, or stabilise it. Partial coalescence of fat droplets in
emulsions or foams (such as whipped cream) can create a fat network that stabilises the
structure. The resulting product is firmer and more stable in time (Drelon et al., 2006).

If the fat phase in an oil-in-water emulsion is really important, the structure can evolve into a
bicontinuous one. Partial coalescence between fat droplets can create a fat network. This
phenomenon can lead to a water-in-oil emulsion or to a bicontinuous system, i.e. water
network and fat network intertwined (Leal-Calderon et al., 2007). Structure of stabilised
emulsion, from particle-stabilised emulsions to bicontinuous emulsions are described by
mathematical models (Jansen and Harting, 2011; Leal-Calderon et al., 2007). However,
bicontinuous structures have not been observed in real food products.

This article will focus on filling ganache for chocolate bonbons. Contrary to fat fillings and
chocolate, ganache contains up to 30% water (coming from cream). The aim of this study was
to investigate the microstructure of ganache, and link it with ganache macroscopic behaviour,
in order to better understand traditional recipes and methods for making ganache. Problems
about ganache can occur during making (such as splitting, i.e. destabilisation that makes
ganache look heterogeneous), or during preservation (such as appearance of a dry or sandy
texture). Besides, it is not always easy to obtain twice the same texture with one recipe of
ganache. Comprehension of microscopic behaviour should help understanding these
variations, as well as errors when making ganache. Understanding ganache microstructure and
texture could also be a key for innovation.

Our hypothesis was that hot ganache is an oil-in-water emulsion. Non-fat cocoa particles
influence emulsion stability, though how is not clear. Upon cooling, cocoa butter crystallises
and partial coalescence takes place between fat globules. Therefore, crystallised ganache is
more a bicontinuous system than a simple emulsion.

To prove these hypotheses, simplified ganache was first studied in order to understand
interactions between ganache components (such as fat, sugar or water). Two types of model
ganache were studied: dark chocolate ganache (made with dark chocolate, water and inverted
sugar) and white chocolate ganache (made with white chocolate, water and inverted sugar).
These ganaches are simplified as water is not usually considered as an ingredient by pastry
chefs, who use cream or milk instead. However, the main components of ganache and
therefore the structure are preserved. Simplified formulation standardised problems due to
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ingredient variability, and simplified the analysis of the role of ingredients in ganache. White
chocolate ganache was used to understand the role of milk components in ganache, while dark
chocolate ganache was used to understand the role of cocoa in ganache behaviour. The
behaviour of non-fat cocoa was studied separately. In this part, ganache macroscopic
behaviour was studied, upon making and cooling. The idea was to link ganache composition
to its properties and texture. Then, real ganache (made with chocolate, cream, inverted sugar
and butter) was studied to confirm hypotheses deduced from the first part of the work. Two
recipes were studied: one for a standard ganache and one for a split ganache. In this part,
microstructure of ganache was studied, upon making and cooling.

1. MATERIAL AND METHODS

2.1 Cocoa solids

Cocoa can be separated into two components: cocoa butter and non-fat cocoa. Cocoa butter is
well known as it has been widely studied (Widlak, 1999; Wille and Lutton, 1966), but it is not
the case for non-fat cocoa. In order to investigate its role in ganache, and more specifically its
interaction with water, non-fat cocoa was manufactured. Cocoa nibs (Valrhona, Tain
l’Hermitage, France) were processed in a screw press (Ecolea, Unieux, France) at 80°C to
obtain cocoa butter and cocoa cake. The cake was processed with a cutter (R2, Robot Coupe,
Vincennes, France) to obtain cocoa powder. Residual cocoa powder fat content was around 12
%.

In order to understand non-fat cocoa interaction with water, a mix of cocoa powder and water
in equal proportions was realised at room temperature (20°C). It was homogenised with a
spoon.

Mixes of cocoa powder, water and sucrose (Baraduc, Lyon, France) in equal proportions were
also realised with different orders of incorporation, at room temperature (20°C):
- 10g cocoa powder and 10g sucrose were mixed, and 10g water was added
- 10g cocoa powder and 10g water were mixed, and 10g sucrose was added
- 10g sucrose and 10g water were mixed, and 10g cocoa powder was added

2.2 Model ganache and design of experiment

Model ganaches were realised by mixing chocolate with an aqueous phase (Figure 1). 400 g
of each ganache were manufactured.

2.2.1 Chocolate

6 dark chocolates and 8 white chocolates were manufactured.

Two premixes were first manufactured. Premix 1 was made with 29.9 % cocoa butter
(Valrhona), 69.7 % sucrose (Baraduc) and 0.4 % soya lecithin (Sunrise, Soya International
Ltd, Cheshire, UK). Premix 2 was made with 29.9 % cocoa butter (Valrhona), 69.7 % whole
milk powder (Choc Armor 26, Armor Protéines, Saint-Brice-en-Cogles, France) and 0.4 %
soya lecithin (Soya International Ltd). Proportions were chosen to maximise sucrose and milk

5
in the premixes, and according to process requirements. A universal conche (MacIntyre,
Arbroath, UK) was used to homogenise and refine the premixes. Conches are surface scraping
mixers used for chocolate manufacture; they ensure aeration of chocolate during mixing to
help flavour development. Premixes were conched for 24 h at 45°C. This process ensured that
mean particle size in the premixes was under 15 µm, so as to match usual chocolate particle
size (Auty et al., 2001). Particle size was measured with a micrometre (Mitutoyo, Roissy,
France).

Dark chocolates were made with premix 1, cocoa liquor (Pure pâte de cacao, Valrhona),
cocoa butter (Valrhona) and soya lecithin (Soya International Ltd). White chocolates were
made with premix 1, premix 2, cocoa butter and soya lecithin. Lecithin was added so that all
the chocolates contained 0.4 % of lecithin, corresponding to a mean percentage for chocolate.

Chocolate composition was chosen according to constrained mixture design (Table 1).
Constraints (limit values) were chosen so as to cover existing chocolates from Valrhona.
For white chocolate, constraints ensured that total cocoa butter was between 25 % and 40 %,
that total sugar was between 20 % and 55 %, and that milk powder was between 20 % and 35
%. For dark chocolate, constraints ensured that total added cocoa butter was between 0 % and
18 %, that total sugar was between 14 % and 49 % and that cocoa liquor was between 38 %
and 82 %. Lecithin proportion was adjusted afterwards to be 0.4 % for all products.
Chocolates were homogenised and stored at 45°C one week before making ganache.

2.2.2 Aqueous phase

Mixes of water (Cristaline, Saint Romain le Puy, France) and inverted sugar syrup (Cremesuc,
Belgosuc, Beernem, Belgium) were realised before making ganache. Six mixes were realised
according to complete block design, with three levels of water and two levels of inverted
sugar syrup. For white chocolate ganache, water/chocolate ratio was 0.25 (low), 0.29
(medium) or 0.33 (high), and inverted sugar syrup/chocolate ratio was 0.11 (low) or 0.21
(high). For dark chocolate ganache, water/chocolate ratio was 0.32 (low), 0.42 (medium) or
0.52 (high), and inverted sugar syrup/chocolate ratio was 0.14 (low) or 0.3 (high). Ratios were
chosen according to existing ganache recipes for framed chocolate candies.

2.2.3 Method for preparing simplified ganache

For each chocolate, 6 ganaches were made. 84 ganaches (36 dark and 48 white) were
manufactured. The aqueous phase was heated to 50°C and added to melted chocolate (45°C).
The mix was homogenised with a hand blender (MD95, Dynamic, Mortagne-sur-Sevre,
France) at 11500 rpm for 30 s. Ganache was then cooled to 35°C (dark chocolate ganache) or
30°C (white chocolate ganache). For each ganache, 40 g were poured in 180 mL sealable cups
(0270044RG, Grosseron, Coueron, France), and stored at 16°C for 48 h.

2.3 “Real” ganache

Standard ganache was made with 49 % chocolate (Manjari 64% from Valrhona), 35 % cream
(Excellence whipping cream, Elle&Vire professionnel, Conde-sur-Vire, France, containing

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35.1% fat and 59.9% moisture), 9 % butter (Extra dry butter 84 % fat, Elle&Vire
professionnel), 7 % inverted sugar syrup (Cremesuc, Belgosuc). Split ganache was made with
55 % chocolate (Manjari 64% from Valrhona), 35 % cream (Excellence whipping cream,
Elle&Vire professionnel) and 10 % butter (Extra dry butter 84 % fat, Elle&Vire
professionnel). For both ganaches, 400 g were manufactured. Cream was heated to 80°C with
inverted sugar syrup, and poured on chocolate at room temperature (20°C). Butter at room
temperature was added when ganache reached 40°C. The mix was homogenised with a hand
blender (MD95, Dynamic) at 11500 rpm for 30 s.

2.4 Instrumental analysis

2.4.1 Water activity (Aw)

Water activity, defined as the partial vapour pressure of pure water, was measured at 25°C (as
advised by AFNOR ISO21807) 48 h after making ganache with a LabMaster-aw (Novasina,
Lachen, Switzerland). Aw was measured three times per product. Mean values were used for
interpretation.

2.4.2 Consistency of hot ganache

Consistency of hot model ganaches was assessed. Indeed, consistency of hot ganache is very
important for pastry chefs when they pour ganache on frames or in hollow forms. After
homogenisation, hot ganache (at 40°C) was sampled in 40 mL cups (VD004, Pro’jet,
Argenteuil, France) and poured over a 50 cm long PVC plane, inclined at 45°. Room and
plane temperatures were 20°C. Distance reached by hot ganache was marked after 45 s (dark
chocolate ganache) or 15 s (white chocolate ganache). As dark chocolate ganache was more
consistent, it flowed more slowly. Distance was linked to ganache yield value: the longer the
distance reached by hot ganache, the lower its apparent yield value. White and dark ganache
were analysed separately for the consistency parameter, as the measured distance was not the
same for both types of ganache. From now on, this parameter is referred to as flow distance.

2.4.3 Penetrometry

Analytical equipment from ThermoFisher Scientific (Waltham, MA, USA) was used to
measure penetrometry. Firmness was measured on crystallised ganache with a Haake Mars III
rheometer, equipped with a 60 mm long, 6 mm diameter stainless steel rod (reference 603-
1002). The stick went down into ganache at 5 mm/min for 10 mm. Normal force was recorded
during all the time the stick went down. Force registration range was between 0.01 N and 50
N. Resolution was 0.001 N. Samples were assessed at 20°C, 48 h after fabrication. They were
taken out of storage room 2 hours before measurement. Each ganache was assessed 3 times.
Mean values of normal force at 10 mm (which corresponded to maximal force measured)
were used for interpretation. From now on, this parameter is referred to as firmness.

2.4.4 Confocal Laser Scanning Microscopy (CLSM)

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Hot ganache and crystallised ganache were analysed by CLSM. Room temperature for
observation was 16°C. Hot ganache was sampled at 40°C a few minutes after
homogenisation. Crystallised ganache was stocked at 16°C after making and sampled one
week afterwards.

To be able to simultaneously observe fat and protein constituents of the food matrix, two
fluorescent dyes supplied by ThermoFisher Scientific with compatible excitation/emission
wavelengths (nm) were used combined with CLSM. Fat (neutral lipids) was stained with the
non-polar Bodipy® 493/503 lipid probes (working solution concentration at 0.5 % w/v in
DMSO). Proteins were stained with the amine reactive dye DyLightTM 550 NHS Ester
562/576 (working solution concentration at 0.5 % w/v in DMSO).

For each condition, approximately 1 mL of sample was gently deposited directly on 50 µL


drop of 1/1 mixed dyes on glass coverslips (0.17 mm thickness). Samples were incubated in
the dark at room temperature (16°C) for at least 10 minutes for staining, then mounted on the
motorised stage of a SP8 AOBS inverted confocal microscope (Leica Microsystems, Wetzlar,
Germany) at the MIMA2 platform (http://www.jouy.inra.fr/mima2/).

HC PL APO CS 40X/0.85 NA dry objective was used with a numerical zoom of 1. 2D


sections were acquired at 600 Hz scan speed with bidirectional scan X direction mode, with a
line average of 4, with 512 x 512 xy image definition (pixel size 569 nm), with a 8-bit
dynamic range per pixel, with pinhole at Airy 1 (99.9 µm diameter) and with a z-step of 1 μm.

For matrix components analysis, Bodipy® was excited at 488 nm using an argon laser (output
power at 30 %, AOTF at 3.5 %) and the emitted “green” fluorescence was recorded from 498
to 556 nm with a PMT detector with a 750 V gain and a -0.1 Offset. DyLightTM was excited
with 561 nm laser diode (AOTF at 2.5%) and the emitted “yellow” fluorescence was recorded
from 571 to 750 nm with a PMT detector with a 750 V gain and a -0.02 Offset.

Image processing was performed with Imaris 8.4 software (Bitplane): fluorescent channels
were merged, “yellow” channels were converted in red (for better visualization), a median
filter was applied, and 2D projections from 3D z-stacks (20 µm above coverslips) were made
with the “Easy 3D Blend” modules.

2.5 Statistical analysis

Statistica 2012 (StatSoft Inc., Tulsa, OK, USA) was used for design of experiment and data
analysis. For analysis, response surface methodology (as done by Almeida and Lannes, 2017)
was used with formulation parameters and instrumental data from model ganaches.

Two ratios were calculated to analyse ganache formulation, using mass contents: Disp and Eq,
defined as follows.

Number Disp = sugar content / water content.

For dark chocolate ganache: Number Eqd = (cocoa butter content + non-fat cocoa content) /
(water content + sugar content)

8
For white chocolate ganache: Number Eqw = (cocoa butter content + milk fat content + milk
protein content) / (water content + sugar content)

Pearson coefficient was used to analyse correlation between formulation parameters (Disp,
Eq) and instrumental data (Aw, flow distance, firmness).

2. RESULTS AND DISCUSSION

3.1 Formulation analysis

3.1.1 Model ganaches vs real ganaches composition

Figure 2 compares the compositions of model ganaches (white and dark) and real ganaches
(standard and split). For model ganaches, it shows the scope of each component for all the
ganaches realised with design of experiment.

Main components in model ganaches were fat (between 22 % and 34 % for dark chocolate
ganache, and between 23 % and 34 % for white chocolate ganache), water (between 24 % and
32 % for dark chocolate ganache, and between 20 % and 24 % for white chocolate ganache),
and sugar (between 16 % and 41 % for dark chocolate ganache and between 33 % and 51 %
for white chocolate ganache). Sugar included sucrose from chocolate, inverted sugar from
inverted sugar syrup and lactose from milk products (milk powder in white chocolate, cream
and butter for real ganache). Ganache also contained non-fat cocoa solids (between 10 % and
25 % for dark chocolate ganache), and milk proteins (between 4 % and 9 % for white
chocolate ganache). For dark chocolate ganache, fat was only cocoa butter. For white
chocolate ganache, fat was a mix between cocoa butter and milk fat (between 19 % and 29 %
of cocoa butter, and between 3 % and 7 % of milk fat).

Real ganache was among the fattest model ganaches realised, but the poorest in cocoa butter
as it contained a lot of milk fat. Indeed, milk fat was not an ingredient in model ganaches, but
its behaviour was supposed to be related to cocoa butter behaviour. Split ganache contained
more fat (cocoa butter and milk fat) and more non-fat cocoa solids than standard ganache, and
less sugar. This difference is due to the fact that model ganaches formulation was based on
balanced ganache recipes.

3.1.2 Behaviour of non-fat cocoa

As non-fat cocoa is one of the main components in dark chocolate ganache (up to 25 % for
the model ganaches realised), it seemed important to understand its behaviour in ganache. In
chocolate, non-fat cocoa particles are dispersed in a fat phase (mainly cocoa butter), together
with sugar crystals. When chocolate is mixed with cream for making ganache, sugar and non-
fat cocoa particles meet water. To understand what happens between components at this stage,
a mix of water and non-fat cocoa was realised, as well as mixes of water, non-fat cocoa and
sucrose.

9
When mixed with water, non-fat cocoa powder swelled. The mix had a dry appearance but
water came out with a little pressure. Besides, the water activity of the mix was 0.95, which
means that non-fat cocoa does not link water strongly.

For mixes of non-fat cocoa, water and sucrose, order of incorporation was tested. When cocoa
powder was added to a mix of water and sucrose (i.e. sugar syrup), cocoa particles did not
swell. This first mix had a humid aspect; it looked like a suspension of cocoa particles in
sugar syrup. However, when sucrose was added to a cocoa and water mix, it had trouble
dissolving: sugar crystals were visible. This second mix had a dry aspect, like the cocoa and
water mix previously realised. Finally, when water was added to a sucrose and cocoa mix, the
result was between the first and the second mixes: sucrose particles dissolved partly but the
mix did not seem as humid as the first one.

After a few hours, the three mixes looked the same: they reached equilibrium. Sugar crystals
were no more visible, but the mixes were thick. Sucrose dissolved completely, and non-fat
cocoa swelled, thickening the mix. It is known from the first experiment (water and cocoa
mix) that cocoa particles swell quickly with water. This second experiment (water, sugar and
cocoa mixes) shows that cocoa particles can also swell with sugar syrup, even if it takes more
time. It is likely that as sugar concentration increases, swelling time of cocoa particles
increases. These experiments highlighted the texturing role of non-fat cocoa, as well as the
importance of order of incorporation on final product texture.

3.1.3 Link between composition and hypotheses about ganache structure

The first hypothesis (cf Introduction) was that hot ganache is an oil-in-water emulsion.
Therefore, it seemed interesting to investigate the continuous phase (water and soluble
components such as sugars), and the dispersed phase (cocoa butter, milk fat and insoluble
components).

3.1.3.1 Continuous phase

To analyse the behaviour of the aqueous phase (and water disponibility), Disp was used.
Viscosity of the water phase depends on sugar molecular concentration (Chirife and Buera,
1997). Dark chocolate ganaches contained sucrose and inverted sugar. Sucrose solubility at
20°C is 2.019 g/mL, and inverted sugar solubility is higher (Boutonnier, 2016). For dark
chocolate ganaches, Disp was never above 2, so the water phase should never have been
saturated in sugar. White chocolate ganaches contained sucrose, inverted sugar and lactose.
Lactose solubility at 20°C is only 0.216 g/mL (Boutonnier, 2016). For white chocolate
ganaches, Disp was sometimes above 2 (the highest was 2.54). Even if the solubility of a mix
of sugars may be higher than the solubility of the sugars alone (Sman, 2017), it seems likely
that the water phase was saturated in sugar for some of the white chocolate ganaches.

3.1.3.2 Dispersed phase

To analyse the behaviour of the dispersed phase, Eqd and Eqw were used. Eq roughly
corresponds to the ratio (equilibrium) between the dispersed phase and the continuous phase.
When mixed, fat and water tend to create emulsions: in this case, according to our hypothesis,

10
droplets of fat in water. Non-fat cocoa and milk proteins are dispersed in the water phase and
could swell or be partially solubilised (proteins). For dark chocolate ganache, the water phase
was not saturated in sugar, so non-fat cocoa particles could swell relatively quickly with sugar
syrup (cf 3.1.2 and McGee, 2007). For white chocolate ganache, milk proteins, even if
sometimes soluble, are treated as dispersed elements in the water phase. Milk proteins, as
macromolecules, are much larger than sugar molecules and their swelling or partial
solubilisation in water could increase ganache viscosity. Besides, milk proteins represented an
average of only 6 % of white chocolate model ganaches.

2.2 Link between ganache composition and macroscopic behaviour

3.2.1 Link between Disp, Eq and instrumental data

Dark and white model ganaches behaviours were analysed separately, using numbers Disp
and Eq. Contour plots of instrumental data (Aw, flow distance and firmness) according to
(Disp, Eq) show clear tendencies (Figure 3, Figure 4).
For all contour plots, interpretation was limited to the parts where instrumental points were
positioned. Results are presented in appendix.

Aw
Contour plots clearly show that Aw is correlated to Disp, for dark chocolate ganaches as well
as white chocolate ganaches. Pearson correlation coefficient between Aw and Disp was -0.94
for dark chocolate ganache and -0.93 for white chocolate ganache. This result is not surprising
as Disp is linked to the quantity of sugar in ganache.

For dark chocolate ganache, non-fat cocoa content increases as Eq increases. The effect of
non-fat cocoa particles on Aw (cf 3.1.2) could explain the slight inclination of level lines for
dark chocolate ganache (Figure 3).

Flow distance
For flow distance, contour plots show clear tendencies: for dark chocolate ganaches as well as
white chocolate ganaches, flow distance increases (i.e. consistency decreases) as Eq
decreases. Pearson correlation coefficient between flow distance and Eq was -0.70 for dark
chocolate ganache and -0.60 for white chocolate ganache.

For dark chocolate ganache, level lines seem to be slightly influenced by Disp: when Eq is
high, flow distance decreases as Disp decreases (left bottom side, Figure 3). In this case,
ganache may be rich in fat and cocoa solids (high Eq) but poor in sugar (low Disp). Cocoa
solids could swell and thicken the ganache (cf 3.1.2). The decrease of flow distance on the
right hand side of the contour plot may not be interpreted as there are no experimental
measures in this zone.

For white chocolate ganache, flow distance clearly decreases as Disp increases. The viscosity
of the aqueous phase is mainly linked to the quantity of sugar, i.e. Disp. If hot ganache is an
oil-in-water emulsion, ganache viscosity is linked to continuous phase viscosity, i.e. Disp.

Firmness

11
Contour plots show that Eq is linked to firmness (force measured with the rheometer).
Pearson correlation coefficient between firmness and Eq was 0.89 for dark chocolate ganache
and 0.79 for white chocolate ganache.

Firmness does not seem to be linked to Disp. For white chocolate ganache, the increase in
firmness for a low Eq and low Disp cannot be interpreted as there are no experimental
measures in this zone. For dark chocolate ganache, the slight inclination of level lines for a
high Eq and high Disp cannot be interpreted clearly as there are no experimental measures in
this zone.

3.2.2 Mapping of ganache behaviour

Model ganache behaviour was described by instrumental analysis. The measure of flow
distance showed how fluid or thick the hot ganache was, while the measure of firmness gave
information about crystallised ganache. Instrumental measures were relevant to describe
ganaches as differences and tendencies were identified using experimental results. During
experimentation, other macroscopic behaviours of model ganaches were noted, such as
splitting for some of the hot ganaches.

All ganaches (white model ganaches, dark model ganaches and real ganaches) were presented
on a single (Disp, Eq) chart (Figure 5). It can be seen that ganaches with a similar behaviour
are gathered. For hot ganaches, thick ganaches (that flow slowly and reach a short flow
distance) had high Eq while fluid ganaches (that flow quickly and reach a long flow distance)
had low Eq. For fluid ganaches, two categories could be observed: liquid ganaches tended to
have low Disp while syrupy ganaches tended to have high Disp. All split ganaches (model or
real) were observed to have high Eq and low Disp. For white chocolate ganaches, all ganaches
that had Disp < 1.8 and Eq > 0.7 were split. For dark chocolate ganaches, all ganaches that
had Disp < 0.8 and Eq > 1 were split. For real ganaches, split ganache had a higher Eq and a
lower Disp than standard ganache. For crystallised ganaches, soft ganaches had low Eq while
firm ganaches had high Eq.

3.3 Ganache microstructure

3.3.1 Microstructure of real ganache

CLSM shows that hot standard ganache (Figure 6, a) is an oil -in-water emulsion. Fat droplets
size is polydisperse, ranging from 1 µm to nearly 20 µm. Fat droplets, stained green, can be
cocoa butter or milk fat. Milk fat can come from butter or from cream, which already contains
polydispersed fat droplets: from 0.1 µm to 5 µm, as observed with a Malvern Morphologi G3
manual microscope.

Crystallised standard ganache (Figure 6, b) is not an emulsion. Fat droplets are connected to
each other and form a fat network (without resulting in an instable ganache). The structure is a
bicontinuous system: the aqueous phase, already continuous for hot ganache, is still
continuous, and the fat phase becomes continuous as a network is created. Red / green ratio
on CLSM images depends on image treatment, as well as fat repartition in the product.
Therefore, the fact that crystallised ganache looks fatter (with more green parts) than hot

12
ganache is not necessarily linked to a difference in ganache composition. Nevertheless, the
difference of microstructure between the two products is significant.

In crystallised split ganache (Figure 6, c), fat droplets appear as deformed connected big
droplets, instead of the regular semi-connected small droplets visible in crystallised standard
ganache (Figure 6, b). Split ganache looks like an oil-in-water emulsion on the point of
getting reversed: CLSM image shows zones of oil-in-water emulsion (bottom) and zones of
water-in-oil emulsion (top) next to each other.

3.3.2 General diagram


Ganache microstructure can be schematically represented as on Figure 7. The graphs
represent the general structure of real ganache:
- when hot: a few minutes after homogenisation. Standard and split ganache are
represented;
- when crystallising: a few hours after homogenisation, with storage at 16°C;
- after crystallisation: a few days after storage at 16°C.
The main components are represented: fat (cocoa butter and milk fat), water, sugar, non-fat
cocoa particles and some of the milk proteins. Whey proteins are not represented, nor are
solubilised sugars.
Hot standard ganache (Figure 7, a) is an oil-in-water emulsion. Sugars, which cannot be seen
on CLSM images, solubilise in the water phase. Inverted sugar is already solubilised in the
cream, and sucrose from chocolate migrates quickly to the water phase. Milk fat from the
cream is already in droplets, stabilised by milk proteins. Cocoa butter forms droplets after the
emulsification step (for instance, homogenisation by hand blender). Non-fat cocoa particles
tend to move from the cocoa butter phase to the water phase.
Upon cooling (Figure 7, c), fat (cocoa butter as well as milk fat) crystallises. The size of fat
crystals on the graph is enhanced compared to reality. Sugar solubilises completely. Non-fat
cocoa particles have migrated to the water phase and start swelling with the remaining free
water.
When ganache is crystallised (Figure 7, d), fat crystals create bridges between fat droplets: it
is partial coalescence. A fat network is created, making ganache a bicontinuous system. Upon
crystallisation, fat droplets shrink. This effect is exaggerated on the graph to enhance the
difference in structure before and after crystallisation. The size of fat crystals is enhanced
compared to reality. Non-fat cocoa particles swell with the remaining free water and help
stabilising the structure.
For split ganache (Figure 7, b), fat droplets are too numerous to be correctly separated by the
water phase and start merging before crystallisation. Besides, split ganache contains less sugar
and more non-fat cocoa particles than stable ganache. Therefore, non-fat cocoa particles tend
to migrate quickly to the water phase, which contains a lot of free water. Thus, the aqueous
phase is thick, which makes it even more difficult for the fat droplets to be separated. The
structure of split ganache is unstable and therefore heterogeneous: it is not an emulsion.

3.4 General discussion

3.4.1 Role of sugar

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Viscosity of the aqueous phase increases while sugar concentration increases. This is why hot
liquid ganaches have low Disp while hot syrupy ganaches have high Disp.

3.4.2 Role of fat

As fat proportion in ganache increases, Eq increases. Previous studies (Brochette, 2013) show
that an emulsion gets thicker when the proportion of dispersed phase increases. Indeed, hot
ganache gets thicker as fat proportion becomes more important, regarding to the aqueous
phase. This is true for dark chocolate ganache as well as white chocolate ganache.

3.4.3 Role of non-fat cocoa

The role of cocoa solids in ganache can be understood by looking at split ganache. When hot
ganache is destabilised, it gets thick and has an oily appearance. This happens when Disp is
low (not a lot of sugar in the aqueous phase) and Eq is high (a lot of fat and a lot of non-fat
cocoa regarding to the aqueous phase). The oily appearance suggests that fat droplets are not
separated anymore by the aqueous phase. This phenomenon has two causes: there is too much
dispersed (fat) phase regarding to the continuous aqueous phase, and the high viscosity of the
continuous phase prevents good dispersion of the fat phase. In the case of split ganache, as the
water phase is poor in sugar (low Disp), there is some remaining free water. This free water is
absorbed by non-fat cocoa particles and the aqueous phase gets thick (cf 3.1.2). The emulsion
is unstable (cf 3.3.1).

On the contrary, if the recipe for ganache is balanced, cocoa solids can help stabilisation.
Cocoa solids thicken the aqueous phase enough to prevent fat droplets from merging
completely: they decrease fat droplets mobility but do not squeeze them into coalescence.
Before crystallisation, non-fat cocoa particles could be seen as Pickering agents that help
stabilising the emulsion.

Balance of dispersed and continuous phase can also be seen through phase volumes. Indeed,
non-fat cocoa particles swelled with water can be seen as a part of the dispersed phase,
creating a more packed dispersed system. It would have been interesting to calculate volume
ratios instead of mass ratios for Eq: volumes would explain more precisely packing inside the
emulsion. However, further studies would have been needed to quantify volumes such as the
swelling of non-fat cocoa particles, or the swelling of milk proteins according to the
remaining free water.

3.4.4 Ganache firmness

Upon cooling, fluid hot ganaches become soft crystallised ganaches and thick hot ganaches
become firm crystallised ganaches. This is greatly linked to fat crystallisation. Indeed, as fat
content (vs aqueous phase content) increases, crystallised ganache gets firmer. Fat in ganache
is composed of cocoa butter and milk fat, therefore it is rather solid at room temperature. As
CLSM images show, crystallised ganache is no more an emulsion: a fat network is created
upon cooling. This network is mostly solid at room temperature, which explains why
crystallised ganache gets firmer when fat content increases. Besides, for dark chocolate
ganache, crystallised ganache gets firmer as non-fat cocoa content increases. Indeed, non-fat

14
cocoa particles thicken the aqueous phase, which is one of the two continuous phases of
crystallised ganache (see 3.3.2).

3. CONCLUSION

A model system of ganache (simplified ganache as used in this study) triggered good
comprehension of ganache structure. The roles of ganache components, especially non-fat
cocoa, have been better understood. CLSM observations of real ganache confirmed
hypotheses that hot ganache is an oil-in-water emulsion, and that ganache upon cooling
becomes a bicontinuous system.

Results could be extrapolated to milk chocolate ganache, a mix between dark chocolate and
white chocolate ganaches. To go further, the effect of process on ganache microstructure and
texture could be studied. For instance, homogenisation could influence texture by reducing fat
droplets size. Temperature control could also impact ganache texture by directing fat
crystallisation.

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ACKNOWLEDGEMENTS

We thank Gabrielle Moulin from AgroParisTech for her advice on sample preparation for
fluorescence observations and Pierre Adenot from MIMA2 plateform for the Imaris computer
station access.

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Figure captions
Figure 1: Graph of model ganache composition (dark and white). For each component, the
minimum and maximum proportions used for experiments are indicated in brackets.
Figure 2: Real ganache (standard and split) compositions compared to dark and white model
ganache compositions. For model ganaches, vertical bars represent minimal and maximal
values for each component, according to design of experiment.
Figure 3: Contour plots of Aw, flow distance, firmness, on (Disp, Eq) plan for dark chocolate
ganache. Dots represent model ganaches made with design of experiment.
Figure 4: Contour plots of Aw, flow distance, firmness, on (Disp, Eq) plan for white chocolate
ganache. Dots represent model ganaches made with design of experiment.
Figure 5: (Disp, Eq) chart with groups of ganaches behaving the same way. Red indications
describe hot ganache behaviour. Blue indications describe crystallised ganache
behaviour. Real ganaches (standard and split) are indicated with crosses (respectively
green and red).
Figure 6: CLSM images of a) hot standard ganache, b) crystallised standard ganache and c)
crystallised split ganache. Fat is stained in green and proteins are stained in red. White
bar shows 50 µm.
Figure 7: Graphs of ganaches before and after crystallisation. On top: hot standard ganache
(left), hot split ganache (right). On the bottom: standard ganache during (left) and after
(right) crystallisation.

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Table 1: White and dark chocolate composition obtained with design of experiment (%).

Cocoa butter Premix 1 Premix 2 Cocoa liquor Lecithin


White chocolate 1 0.00 71.00 29.00 0.00 0.00
White chocolate 2 0.00 50.00 50.00 0.00 0.00
White chocolate 3 14.28 56.68 28.98 0.00 0.06
White chocolate 4 14.28 35.69 49.97 0.00 0.06
White chocolate 5 0.00 60.5 39.5 0.00 0.00
White chocolate 6 7.14 63.84 28.99 0.00 0.03
White chocolate 7 7.14 42.84 49.99 0.00 0.03
White chocolate 8 14.28 46.19 39.48 0.00 0.06
Dark chocolate 1 0.00 19.93 0.00 79.73 0.33
Dark chocolate 2 11.96 19.93 0.00 67.77 0.33
Dark chocolate 3 0.00 59.9 0.00 39.93 0.17
Dark chocolate 4 0.00 39.9 0.00 59.85 0.25
Dark chocolate 5 5.98 19.93 0.00 73.75 0.33
Dark chocolate 6 5.98 39.9 0.00 53.86 0.25

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