Key microstructural and rheological
parameters underlying the
functionality of roll-in shortenings
A.G. Marangoni, B. Macias Rodriguez, F.M. Peyronel
University of Guelph, ON, Canada
2
TAG MOLECULES
Structural hierarchy in fats
Acevedo and Marangoni. (2010). Cryst. Growth. Des (10): 3327-33
Roll-in Shortening
• Stiff but plastic fats used in the manufacture of puff-pastry
• High trans (TFA) and saturated (SFA) fatty acids content
66% SAFA+TFA (w/w) (risk of cardiovascular health)
3
Microstructure, Mechanical and Physical Properties of Roll-in Shortening
• Microstructure: 3-D network
structured by primary and secondary
interactions
• Yield value criteria for roll-in
shortenings (Haighton 1959): 800-
1600 (g/cm2) : puff pastry.
Shortening A: fully crystallized in line, B: partially. Adapted from:
Heertje. (2014). Food Struc.
Strain ()/ln (ho/h)
Str
ess
()/
kP
a
A
B
1
2
4
A B
Research Justification and Question
• Limited understanding of the structural and physical properties governing the mechanical behavior (“functionality”) of roll-in shortenings.
• Attempts to reduce SAFA and TFA in roll-in shortenings unsatisfactory (brittle/soft).
• Global trend to reduce SFA and TFA
5
Which rheological property determines the functionality
of roll-in shortening?
Shortening name Manufacturer Composition
Puff-flake (hydrogenated) (1) Bunge Hydrogenated soybean oil and
cottonseed oil
SPS NH special pastry (non-
hydrogenated) (2)
Bunge Canola, modified palm and palm
kernel oils
SPS special pastry (3) Bunge Hydrogenated vegetable oil and
modified
All-purpose (4) Palm oil and modified palm
For pays (5) Bunge Interesterified soybean oil
All-purpose (6) ADM Interesterified soybean oil
Icing (7) Cargill Palm oil
*-shortening (8) In-house Hydrogenated soybean oil, soybean
oil, glycerol monopalmitate
6
Shortening Used in Study
*Used only for rheological characterization
7
Shortening Description
1 Roll-in hydrogenated soybean and
cottonseed oils
2 Roll-in non hydrogenated canola oil,
modified palm and palm kernel oils
3 Roll-in hydrogenated vegetable and
modified palm oils
4 All-purpose non hydrogenated palm and
modified palm oils
5 Pays interesterified soybean oil
6 Cake interesterified soybean oil
7 Icing palm oil
8 *Fully hydrogenated soybean oil,
soybean oil and glycerol monopalmitate.
Fatty acid composition
8
Fatty acid Sample
1 2 3 4 5 6 7
12:0 5.0
14:0 2.5 1.1 1.1
16:0 13.3 30.0 20.5 45.1 11.4 12.4 45
18:0 16.7 3.4 13.4 4.8 31.2 33.6 5.1
18:1 (c9) 25.9 40.4 27.9 39.2 17.5 16.5 39.0
18:1 (t9) 9.5 13.9
18:2 (t9, 12) 19.8 8.9
18:2 (c9, 12) 13.7 12.5 14.7 9.9 35.1 33.9 8.9
18:3 (3) 1.1 6.2 0.8 4.8 3.6
SFA+TFA 59.3 40.9 56.7 51 42.6 46 51.2
Melting and SFC profiles
9
Data sets colored red correspond to roll-in shortening
A
B
0 10 20 30 40 50 600
10
20
30
40
50
60
1
2
3
4
5
6
7
Temperature (°C)
SF
C (
%)
10 20 30 40 50 600
2
4
6
51.8
47.9
50.4
44.3
52.8
50.8
41.6
Temperature (C)
He
at
flo
w (
W/g
)
1
2
3
4
5
6
7
Polymorphism (WAXS)
10 15 20 25 30
0
5000
10000
15000
'
> '
'>
'
'
'>
'>
2 ()
4.24.6
3.83.6
1
2
3
4
5
6
7
Inte
ns
ity
(a
.u.)
B
Mechanical properties: small deformation
Test conditions
Sample (201.5 mm DIAthickness)
Loading (3 N force control)
Sand blasted plate-plate geometry
Input: (0.001-100%) (= 6.28 rad/s)
Output: G’, G’’, * when G’ decreases 5%
(ISO 6721-10)
𝐽 𝑡 = 𝐽0 + 𝐽1 1 − 𝑒𝑥𝑝 −𝑡
Λ+
𝑡
𝜂0
Rotational rheology
(Creep and recovery) Oscillatory rheology
Test conditions
Stress step: 200 Pa (within LVR)
Loading/unloading time: 5/10 min
Burger Model
𝐽 𝑡 = 𝐽𝑚𝑎𝑥 − 𝐽0 − 𝐽1 1 − 𝑒𝑥𝑝 −𝑡
Λ
Creep
Recovery 11
J0
J1
0
t1 t2 t3 t4
J
Jmax
S1
D2
S2
D3
Small deformation rheology
12
G’: Elastic modulus, and *: yield stress. Data sets colored red corresponded to
roll-in shortenings.
1 2 3 4 5 6 7 80
200
400
600
800
aa
a
b
cc
a
b
Sample
* (P
a)
1 2 3 4 5 6 7 80
1000
2000
3000
4000
a,c
b
c,d
b
aa,c
bb,d
Sample
G' (k
Pa
)
A B
Creep and recovery
13
J0 10-7 (Pa-1) J1 10-7 (s) 0 108 (Pa s)
1 7.40.4 3.70.9 27.17.1 4.60.5
2 4.61.8 2.21.0 21.75.0 9.831.9
3 5.71.8 2.20.7 16.21.34 12.52.0
4 12.60.8 12.92.3 18.12.4 1.60.2
8 6.71.4 2.00.7 14.34.7 6.51.7
0 200 400 600 8000
2.0×10 -6
4.0×10 -6
1
2
4
8
3
t (s)
J (
Pa
-1)
J0, J1: instantaneous and retarded compliance, : retardation time,
0 : zero-shear viscosity
14
Mechanical properties: large deformation
Uniaxial compression Cone penetrometry
𝜺𝒉 = 𝟏
𝒉
𝒉
𝒉𝟎
𝒅𝒉 = 𝒍𝒏𝒉
𝒉𝟎
𝝈 =𝑭
𝑨
0.2 0.4 0.6 0.80
20
40
60
80Eapp
y
h
(
kP
a)
𝜀 ℎ = 0.125 𝑠−1 (strain rate)
Test conditions
2010mm (DIAthickness)
70% compression, 16 °C
Test conditions
𝐶 = 𝐾𝑊/𝑝1.6
AOCS method Cc 16-60
Large deformation rheology
15
0
20
40
60
80
(
kP
a)
0.2 0.4 0.6 0.8h
0.2 0.4 0.6 0.80
20
40
60
80
h
(
kP
a)
Roll in All-purpose
Interesterified Icing
: true stress, h: true strain.
16
Large deformation rheology
Eapp: apparent Young modulus (kPa), *: yield stress, C: yield value.
Data sets colored red correspond to roll-in shortening
A
1 2 3 4 5 6 7 80
2
4
6
8
a
b
a
c
d
a
b
a
Sample
*(
kP
a)
1 2 3 4 5 6 7 80
5
10
15
C (
kP
a)
a aa
b
c
a
dd
Sample
B
C
1 2 3 4 5 6 7 80
2
4
6
8
10
a,c,e
b
a,d
a,b
a,d
c,da,d
b,e
Sample
Ea
pp
Strain sweep of an all-purpose shortening at a fixed frequency (6.28 rad/s). Small amplitude
(SAOS) and large amplitude oscillatory rheology (LAOS). Lower left inset 1: linear region, 2: non
linear region, 3: stress overshoot, 4: plastic flow
Rheological Properties
17
SAOS
LAOS
Lissajous curves (Linear regime)
Large Deformation Rheology
19
Elastic moduli
𝐺′𝑀 ≡ⅆ𝜎
ⅆ𝛾 𝛾=0 = 𝑛𝐺′
𝑛 = 𝑒1 − 3𝑒3𝑛 𝑜𝑑𝑑
+⋯ ,
𝐺′𝐿 ≡𝜎
𝛾 𝛾=±𝛾0 = 𝐺′
𝑛 −1 𝑛−1 /2 = 𝑒1 + 𝑒3𝑛 𝑜𝑑𝑑
+⋯ ,
Viscous moduli
𝜂′𝑀 ≡ⅆ𝜎
ⅆ𝛾 𝛾 =0 =
1
𝜔𝑛 𝑛𝐺′′
𝑛 −1(𝑛−1)2 = 𝑣1 − 3𝑣3
𝑛 𝑜𝑑𝑑
+⋯ ,
Dynamic viscosity
𝜂′𝑀 ≡ⅆ𝜎
ⅆ𝛾 𝛾=0
=1
𝜔𝑛𝐺"
𝑛(−1)(𝑛−1)/2= 𝑣1 − 3𝑣3
𝑛 𝑜𝑑𝑑
+⋯ ,
𝜂′𝐿 ≡𝜎
𝛾 𝛾=±𝛾0 =
1
𝜔𝐺"
𝑛 = 𝑣1 − 3𝑣3𝑛 𝑜𝑑𝑑
+⋯ ,
, 𝜸
Fig 7. Illustration of viscoelastic moduli
𝜂′𝐿 ≡𝜎
𝛾 𝛾 =±𝛾 0 =
1
𝜔𝑛 𝑛𝐺′′
𝑛 = 𝑣1 + 𝑣3𝑛 𝑜𝑑𝑑
+⋯ ,
Source: Ewoldt et al., (2008)
20
Lissajous curves of shortenings. Lower insets share the same aspect ratio of sample 1.
1) Roll-in, 2) All-purpose, 3) Interesterified
-4000
-3000
-2000
-1000
0
1000
2000
3000
4000
-0.02 -0.01 0.00 0.01 0.02 -0.003 -0.001 0.001 0.003
-1200
-700
-200
300
800
-0.04 -0.02 0.00 0.02 0.04
1 2
3
Lissajous curves (linear-to-nonlinear)
Thixotropy
Fig 6. Thixotropy. 1: Constant deformation (CSD) at = 6.28 rad/s and = 0.001% (in LVR),
2: CSD at same and =5% (out LVR). 3: CSD as interval 1.
t1 t2 t3
G’
1
2
3
21
22
Figure 12. Thixotropic behavior of selected shortenings (structural regeneration phase) .
: SPS NH special pastry G’0 = 3546 kPa, recovery: 93%, : All-purpose G’0 = 3862 kPa,
recovery: 82% .
0
1000
2000
3000
4000
0 50 100 150
G'
(kP
a)
t(s)
23
~50 kPa
Rheological Behavior under different normal forces
Viscoelastic properties of roll-in shortenings at increasing pressures.
Yield zone: from * to G’=G’’. Lower left inset shows a sketch of roll-in sheeting.
24
Strain-stress curves of selected shortenings at a fixed frequency (6.28 rad/s). Roll-in:
Shortening SPS.
Stress overshoots and brittleness/plasticity
Structural Origins of Rheological Behavior?
Scattering
Atomic features 1-20 Å
~1 105Å or 10 µm
~200Å or 0.02 µm
?
26
Aggregation? Fractal? size?
More
aggregation?
USAXS
length scale =2 π
q
X-Ray Scattering
Scatterer Shape? Size?
Molecular features ~150 Å
USAXS reveals nanocrystal fractal aggregation for SSS in OOO
27
M.F. Peyronal et al. 2013, Applied Physics Letters M.F. Peyronal et al. 2014, J. Physics: Condensed Matter M.F. Peyronel et al. 2014, Current Opinion in Colloid and Interface Science M.F. Peyronel et al. 2014, Food Biophysics M.F. Peyronel et al. 2015, Applied Physics Letters D.A. Pink et al. 2015, J. Physics D: Applied Physics
Fat polycrystal formation is similar to a colloidal aggregation process
28
D.A. Pink et al., 2013, J. Applied Physics Quinn, B. et al., 2014. J . Physics : Condensed Matter
Physical Structural Levels in Fats
29 Peyronel et al. 2014- Lipid Technology , 2014
Surface Morphology Ds
Dm Dm = 1
D
USAXS of shortening
30
1, 2 and 3: roll-in shortenings. 4: all-purpose shortening. P
Sample P1 Rg1 P2
Rg2
1 3.90.1 62260.5 1.70.0 8024403
2 3.70.0 76053.5 2.60.1 48121734
3 3.70.0 54036 2.10.1 4162.51776
4 3.70.0 8040630 - -
0.0001 0.001 0.01 0.1
100
105
1010
1234
q[Å-1]
Inte
ns
ity
lo
g I(q
) [c
m-1
]
Acknowledgements
Natural Sciences and Engineering Research Council
Canada Research Chairs Program
Ontario Ministry of Agriculture and Food
Coasun Inc.
Thank You!
Thank You!