Entropy-driven

engineering of the yield

stress of fats
Alejandro Marangoni1, Nuria
Acevedo1,2
1Department of Food Science
University of Guelph
2Department of Food Science

Iowa State University

 2
Marangoni et al., 2012, Soft Matter
 Structural Hierarchy in Fats (1997)
Rheology
Mechanical Strength Fat
Sensory Impressions
Macroscopic World
>0.2mm

Crystal Network

Heat, mass, momentum transfer

Solid Fat Content

Microstructure
Crystal Clusters
0.1-200m
Heat, mass, momentum transfer

Polymorphism Crystals

Heat, mass, momentum transfer Nanostructure

0.4100nm
Molecular Structure Triacylglycerol Molecules
3
 Structural-mechanical fractal model
Fractal Floc

Link

Particle

Marangoni, 2000, Phys. Rev. B 62, 13951

Marangoni and Rogers, 2003, Appl. Phys. Lett. 82, 3239
Narine and Marangoni, 1999, Phys. Rev. E 60, 6991
Narine and Marangoni, 1999, Physical Review E 59: 1908
 Fat Crystal Network Model
Hamaker Constant

A
G'
1 1
3-D
3D

6 a d 2
0

SFC/100
Variables Explanation
Experimental value, obtained
from a ln G vs. ln plot
a diameter of primary particles
Strain at the limit of linearity
d0 separation between the flocs

5
Structural hierarchy in fats (2010)

Acevedo et al., 2011. Current Opinion in Colloid and Interface Science 6

 Cryo-TEM: Sample preparation

Fat : isobutanol
Mixer Vacuum filtration
(~1:50)

Fat crystal
resuspension

Mixer

Homogeneous
Cryo-TEM sonication
Suspension

7
 100%S

PLATELETS

Acevedo and Marangoni, 2010a, Crystal Growth and Design 8

 SCHERRER ANALYSIS
UNIT CELL SUBCELL

lamella

K
D=
FWHM cos

D = Domain size or crystal thickness

K = Crystal shape factor
= X-Ray wavelength
FWHM = Full width at half maximum
=diffraction angle
9
100%S

Platelet thickness
Cryo-TEM= 4.23 0.76nm
XRD= 4.5 nm 10
11
12
13
 Fat crystal network nanoscale is
strongly affected by supersaturation
and external fields and additives

Acevedo and Marangoni, 2010b, Crystal Growth and Design

Acevedo et al., 2012, Faraday Discussions
14
Acevedo et al., 2013, Food and Bioprocess Technology
Supersaturation Effects

30% S 50% S

15
100% S
Quantified manually using Image J

16
 Effects of external fields on the nanostructural level
100%FHCO-NI 100%FHCO-CI

static static

100%FHCO-NI 100%FHCO-NI

under shear fast cooling

17
Chemical interesterification,
supersaturation
and shear effects

18
Cooling rate effects

19
Effect of supersaturation and external fields

20
Shear or cooling rateyour choice

21
 Platelet dimension interrelationships
400

y = 2.3 x 10.7 (R2=0.98)

Platelet length (nm)

300

200

100
Platelet lengths are
~ twice the widths
0
60 80 100 120 140 160
Platelet width (nm)

400 length y = 26.7 x 689

Prediction of
R2=0.94
Platelet size (nm)

300 platelets
size from the
200
y = 11.3 x 277.5 value of the
width thickness
100 R2=0.90
30 32 34 36 38 40
Crystal thickness (nm)
22
 Meso vs. Nano

Equivalent Diameter , m

Equivalent Diameter , nm
300
3

2 200
Unit-nanocrystal

Unit-microcrystal

1 100
0 20 40 60 80 100
% S, w/w
23
Fat polycrystal formation is similar to a
colloidal aggregation process

D.A. Pink et al., 2013, J. Applied Physics, submitted

24
USAXS reveals nanocrystal fractal
aggregation for SSS in OOO

M.F. Peyronel et al., 2013, J. Applied Physics (submitted) 25

 Can we deliver improved
functionality of fat by modifying the
properties of the nanoscale?

26
roll-in shortening

27
 The shortening

0.46 nm
0.39 nm
Intensity, au

0.37 nm

16 18 20 22 24 26 28 30 32 34
2
28
 APPS Our GMP GMS BFP APPS Our GMP GMS BFP
Fatty Acid Fatty Acid
shortening shortening

14:00 0.20 0 1.25 0 0 20:00 0.42 0.28 0.50 0.58 0.58

18:3n6 0 0.15 0 0 0
16:00 12.35 11.08 57.39 11.16 11.50
20:1c11 0 0 0 0 0
16:1c9 0.07 0 0 0 0
18:3n3 0.31 4.88 0 0 0
17:00 0.18 0.12 0 0.25 0.30
18:2tt CLA 0 1.06 0 0 0
18:00 18.20 25.75 38.21 87.57 86.40
22:00 0.33 0.24 0 0.33 0.3
18:1t4 0.02 0 0 0 0 24:00 0 1.21 0 0 0
18:1t5 0.27 0 0 0 0 22:5n3 0 1.46 0 0 0
18:1t6-8 0.48 0.09 0.12 0 0.03 Trans fat
29.20 3.70 1.18 0 0.50
18:1t9 3.37 0.13 0.24 0 0.05 content
18:1t10 4.19 0.28 0.42 0 0.11
18:1t11 6.40 0.36 0.06 0 0.04
18:1t12 3.18 0.10 0.23 0 0.05
18:1t13 4.42 0.16 0.11 0 0.05
18:1c6-10 20.65 13.63 1.22 0.11 0.23
18:1c11 2.42 1.07 0 0 0.05
18:1c12 6.71 0.79 0 0 0.08
18:1c13 0.91 0.19 0 0 0
18:1c14 0.29 0.12 0 0 0
18:2tt 0.94 0 0 0 0
18:2t9&12 1.11 0.24 0 0 0.06
18:2c9t13 0.57 0.34 0 0 0.11
t,t 1.35 0.20 0 0 0 29
18:2c9-t12 1.61 0.41 0 0 0
30
 Glyceryl
Monostearate
(GMS)

Sorbitan
Monostearate
(SMS)

Polyethylene Glycol
Sorbitan
Monostearate
-Tween 60-
(PGMS)
Glyceryl
Monopalmitate
(GMP)
Sorbitan
Monopalmitate
(SMP)

Sodium Stearoyl
Lactylate
(SSL)

Phosphatidylcholine
(P-CHOLINE)

(BFP-75) Caravan Mono and Di Glycerides from hydrogenated palm fat 31

75 BFP
 Crystallization in a votator
FULLY HIDROGENATED SOYBEAN OIL (FHSO) SOYBEAN OIL (SO)

10:90 40:60 (w/w)

Votator Configurations No Emulsifier 1% and 3% Emulsifier

1. GMS (Glyceryl Monostearate)

VOTATOR LINE 2. SSL (Sodium Stearoyl Lactylate)
3. SMS (Sorbitan Monostearate)
4. PGMS (Polyethylene Glycol
UNIT A UNIT B UNIT C Sorbitan Monostearate)
VESSEL PUMP -2oC 15oC 10oC
5. P-CHOLINE (Phosphatidylcholine)
6. BFP (Mono and Di Glycerides from
hydrogenated palm fat)
7. SMP (Sorbitan Monopalmitate)
SAMPLE AB 8. GMP (Glyceryl Monopalmitate)

A and C: scraped surface chillers SAMPLE ACB

SAMPLE ABC
B: working unit

CONTROL: HIGH SATURATED AND

75 SAMPLES TRANS FAT
ROLL- IN SHORTENING

ANALYSIS 32
MATERIALS AND METHODS

Rheological Properties Small Deformation Tests

Thermal Properties Differential Scanning Calorimetry (DSC)

ANALYSIS Solid Fat Content (SFC )

Physical Properties Oil Binding Capacity (OMG)

Microstructure Polarized Light Microscopy (PLM)

Powder X-ray Diffraction (SAXD, WAXD)

Nanostructure Cryo-TEM

33
 FHSO:SO PROPORTION
OIL BINDING
FAT MIXTURE 10:90 20:80 30:70 40:60
NO EMULSIFIER AB 8.6 2.0 0.6
NO EMULSIFIER ABC 6.8 2.4 1.4
NO EMULSIFIER ACB 27.8 19.7 5.9
1%GMS AB 36.9 7.7 1.8
1%GMS ABC 32.7 8.6 2.9
1%GMS ACB 35.6 7.6 2.6
3%GMS AB 7.4
3%GMS ABC 31.0 5.0
3%GMS ACB 34.0 15.4
1%SSL AB 30.6
1%SSL ABC 34.6 21.1 9.4
1%SSL ACB 30.7 18.3 10.2
OIL MIGRATION (%) 3%SSL AB 45.4 SHORTENING
3%SSL ABC 30.5 19.8 9.8
3%SSL ACB 41.7 33.5 11.8 CONTROL
1%SMS ABC 19.5 11.3
1%SMS ACB 14.2
3%SMS ABC 38.5 7.8
3%SMS ACB 17.7
1%PGMS ABC 17.0 6.6
1%PGMS ACB 12.5 6.1 2.8 %
3%PGMS ABC 22.6 13.1
3%PGMS ACB 19.1 13.3
1%P-CHOLINE ABC 7.9
1%P-CHOLINE ACB 7.1
3%P-CHOLINE ABC 11.6
3%P-CHOLINE ACB 12.1
1%BFP ABC 5.8
1%BFP ACB 6.9
3%BFP ABC 11.6
3%BFP ACB 10.4
1%SMP ABC 15.2
1%SMP ACB 5.6
3%SMP ABC 15.7
3%SMP ACB 7.8
1%GMP ABC 3.1
1%GMP ACB 3.8 34
3%GMP ABC 28.3
3%GMP ACB 7.3
 G' (MPa)
NO
EM
UL

0.0
0.5
1.0
1.5
2.0

SI
F
1% IER
G

BFP
1% MS

GMP
GMS
3% S
S
1% SSL
1% 3% P L
G
3% P PG M
-C S

1% P-CHOLINE
RHEOLOGICAL PROPERTIES

P- H MS
CHOL
O IN
L E
1% INE
3% B
FP
ABC

1% BFP
3% G
M
G P
1% MP
3% S
M
SMP
1

Control
NO % P
EM 3% SM
UL SMS
SI S
F
1% IER
G
1% MS
3% S
S
1% SSL

1% BFP
1% 3% P L
G
3% P P M
-C G S
P- H MS
CHOL
O IN
L E
P-CHOLINE
1% INE
3% B
ACB

FP
1% BFP
3% G
M
G P
1% MP
3% S
M
S P
Co MP
nt
ro
l
Control
30:70

35
 * (Pa)
NO
EM

0
300
600
900
1200
1500

UL
SI
FI
1% ER
G
1% MS
3% SS
1% SSL
L
RHEOLOGICAL PROPERTIES

1% 3% PG

1% GMP
GMS
3% P- PG S M
P-CHO MS
CH L
OLINE
1% INE
3% BF
P
1% BFP
ABC

3% GM
G P
1 % MP
3% SM
S P

Control
NO 1% MP
EM 3% SM
UL SMS
SI S
F
1% IER
G
1% MS
3% SS
1% SSL
L

BFP
1% 3% PG

1% GMP
P M
3% P- G S
P-CHO MS
CH L
OLINE
1% INE
3% BF
P
1% BFP
ACB

3% GM
G P
1 % MP
3% SM
Control

S P
Co MP
nt
ro
l
30:70
 NO Equivalent Diameter ( m)
EM
UL

0.0
0.5
1.0
1.5
2.0
2.5
SI
F
1% IER
1 % GM
Control

3% S S
1% SSL
1% 3 S
3% P % PG L
P M
P--CH GMS
CHO S
OLIN
1%LINE
3% B E
1% BFFP
ABC
3% G P
M
1% GM P
MICROSTRUCTURE (PLM)

3% S P
NO M
1% SMP
EM 3% S P
UL SMS
SI MS
1%FIE
R
1 % GM
3% S S
1 % SS L
1% 3 S
3% P % PG L
P M
P--CH GMS
CHO S
OLIN
1%LINE
ACB

3% B E
1% BFFP
3% G P
M
1% GM P
3% S P
M
Fat blend

Co SMP
100m
30:70

nt P
ro
l
Control

Fat blends
Diameter
Equivalent

GMP
< Control

Eq. Diam
2.35 0.51 m

37
 PLM
Equivalent Diameter ( m) Equivalent Diameter ( m)
ab
1%

0.0
0.5
1.0
1.5
2.0
2.5
40

0.0
0.5
1.0
1.5
2.0
ab GM 40 -60 2.5
1 S -6 a
ab % 0 b
3 SS ab
ab % S L 30 c
c S -7
ab 1% L 30 0
c G - a
3% M 30 70 b
ab G S
c M -7 ab
ac 0 c
b ab 1% S
N c S ac
O 3 S 20 b
EM % S L
U SL
L
20 -80
ac SIF
-
b IE 20 80 ab
ac 1% R -8 ab
b G 0 c
3% M ac
ac G S 10 b
b M -9
ac 1% S 0
b S C ac
3% S
L O b
C SS N
O TR
N L
NO EMULSIFIER

TR O
O
L 10:90 L

N
Equivalent Diameter ( m) Equivalent Diameter ( m)
O N
EM O
EM

0.0
0.5
1.0
1.5
2.0
2.5

U
0.0
0.5
1.0
1.5
2.0
2.5

LS U
LS
IF IF
I ER I ER
1%
G 1%
M G
M
3% S S
G 3%
M G
S M
S
1%
SS 1%
3% L SS
SS L
L 1%
3% PG
PG M
M S
S
1%
1%
SM
SM
S
3% S 3%
SM SM
S S

C C
20:80 acb
20:80 abc

on on
tr tr
ol ol
38
NANOSTRUCTURE

FHSO:SO SHORTENING 39
CONTROL
 SAXRD
Cryo-TEM
NO
Domain Size () NO Nano-equivalent Diam. (nm)
EM
EM
UL UL

0
50
100
150
200
250
300
350
0
50
100
150
200
250

SI SI
FI FI
1% ER E
NANOSTRUCTURE

G 1% R
1% M S
3% S G
S 1% MS
1% SSL
1 % 3% P L
3% P P M G 1% SSL
- G
P-CH MS PG
CHOL S
OLIN
E
M
1% INE 1% S
3% B
F
B
1% BFP 1% FP

30:70
3% G P GM
GM P 1% P
1% M P AB
3% S
M SM
S P
NO
30:70 ABC

NO 1% M P EM 1% P
EM 3% SM AB UL SM
UL SMS C A S
SI S
F N B SI
1% IER AC O E 3%FIE
B M GR

ABC
3%GM
G S NO UL M
1% M S S
3% S EM SIF
S
1% SSL AC UL IER
3%PG L B SI
PGMS 1% FIE
1% M S G R
20:80

20:80

3% S CO M
CO SMS NT S
NT MS RO
RO
L L
ratio
BFP

SMS
GMP
GMS
Fat blends

1% PGMS

Length/With

Fat blends
< Control

Eq. Diam.

Control = 4

Control
Fat blends = 2.5 3.5

40
 Diffusion Coefficient, D (x 10-12 m2/s) OMG(%)
@ 4 C @ 18 C @ 20C
name
number D = 41 ms D = 61 ms D = 41 ms D = 61 ms
8 30-70 ABC NO EMULSIFIER 5.7 4.8 7.7 6.9 2.4

10 20-80 ABC NO EMULSIFIER 5.9 4.8 8.3 7.6 6.8

11 20-80 AB NO EMULSIFIER 3.1 3.1 5.8 5.6 8.6

14 40-60 ABC NO EMULSIFIER 4.8 5.4 7.3 6.5 1.4
18 30-70 ABC 1% GMS 5.8 4.7 8.1 7.2 2.9
25 20-80 ACB NO EMULSIFIER 6.1 5.2 8.5 7.5 19.7
43 30-70 ABC 1% SSL 5.5 5.0 8.1 7.4 9.4
50 30-70 ABC 1% SMS 3.3 2.8 5.7 5.2 11.3
52 30-70 ABC 1% PGMS 5.6 4.7 8.5 7.3 6.6
54 30-70 ABC 1% P-CHOLINE 5.6 4.9 8.1 7.3 7.9
56 30-70 ABC 1% BFP 4.9 5.0 8.2 7.5 5.8
58 30-70 ABC 1% SMP 6.1 5.1 9.5 8.3 15.2
60 30-70 ABC 1% GMP 5.4 5.1 7.9 6.7 3.1
REFERENCE SHORTENING 1.59 0.05 3.03 0.13 2.8

41
The case of GMP addition

42
43
44
Average of the 63 enthalpies of melting = 30.7 kJ/mol
45
Temperatures normalized to 37oC 46
47
48
 Microscopic World
S k B ln W
n!
W
(n k )!
S is the configurational entropy for mixing k imperfections into n
lattice sites. W is the number of permutations of k in n, where
order is important.

WS 2
SS 2 SS1 kB ln WS 2 kB ln WS1 k B ln
WS1
49
Permutations and NOT combinations

n VSSS GMP vSSS

n!
W
(n k )! k (VSSS GMP VSSS ) vSSS

VSSS GMP !
WSSS GMP
VSSS !

50
 Stirling Approximation yields:

ln WSSS GMP VSSS GMP ln VSSS GMP VSSS ln VSSS

For a perfect (GMP) crystal without impurities

VSSS GMP VSSS WSSS 1

51
 Macroscopic World - melting
H m
S m
Tm

S m S L S S

S m ,1 S m ,2 ( S L1 S S 1 ) ( S L 2 S S 2 )
( S S 2 S S 1 ) ( S L1 S L 2 )
52
 Macro-micro proposal

S SSS GMP S SSS k B ln WSSS GMP Sm ,SSS Sm ,SSS GMP

53
54
Nice Lift!

55
 Food and Soft Materials Science Lab
Canada Research Chair in Food, Health and Aging
Food and Soft Materials Science Laboratory
University of Guelph
Graduate Students:
Terri Stortz, Ph.D.
Laboratory manager and Research Associate:
Alex Zetzl, Ph.D.
Fernanda Peyronel
Fan Wang, Ph.D.
Collaborators and their teams: Fernanda Peyronel, Ph.D.
David Pink theoretical physics, St. Francis Xavier Braulio Macias, Ph.D.
Stefan Idziak experimental physics, Waterloo John Wood, M.Sc.
Gianfranco Mazzanti chemical engineering, Dalhousie Anitta Sebastian, M.Sc.
Nuria Acevedo nanotechnology, Iowa State Alexia Blake, M.Sc.
Shai Barbut meat science, Guelph Chloe OSullivan, M.Sc.
Douglas Goff frozen systems, Guelph Rong Liu, M.Sc.
Rodrigo Campos cocoa butter crystallization, MARS
Yukihiro Miyazaki wax crystallization, KAO Postdoctoral Fellows:
Research Assistants: Maya Davidovich Pinhas
Saeed Mirzaee Ghazani Spin-off companies:
Edmund Co Coasun, Inc.
Andrew Gravelle 56
 Funding Agencies
Natural Sciences and Engineering Research Council
Canada Research Chairs Program
Ontario Ministry of Agriculture and Food
Coasun Inc.
Two recent books -2012

58
Thank You!

Thank You!
Isolated System?
NVT ensemble

60
Microcanonical Ensemble = Statistical Ensemble of
Isolated Systems

61
Representation of the different structural levels present
in a fat crystal network

Sn-2

Tuning fork

Sn-1 Sn-3

Molecule
62
Acevedo and Marangoni, Crystal Growth and Design, 2010a
 Physical Properties Rheological Thermal Properties
Microstructure Nanostructure
Properties
OMG SFC 20C G (MPa) * (Pa) Tm Hm Eq.D EqD L/W Polymorphic
(%) (%) (C) (J/g) (m) (nm) ratio form

CONTROL 2.8 36.7 1.0 835 50.5 44.9 2.3 247 4

40:60 ABC 1.4 35.72 4.4 1075 62.9 75.0 1.4 215 2.5

30:70 AB 2.0 31.74 2.4 1191 61.6 66.4 1.6 ND ND

30:70 ABC 2.4 30.08 2.2 952 61.7 61.0 1.3 133 2.7

30:70 AB 1%GMS 1.8 29.80 1.8 1095 61.0 61.9 1.2 116 2.8
30:70 ABC
2.9 28.66 1.7 1010 60.6 57.9 1.1 155 3.3
1%GMS
30:70 ACB
2.6 29.76 2.1 1292 61.0 58.7 1.1 105 3
1%GMS
30:70 ABC
3.1 30.84 1.8 891 56.4 34.39 1.3 180 2.4
1%GMP
30:70 ACB
3.8 30.24 1.9 789 55.0 35.5 1.6 ND ND
1%GMP
30:70 ABC
7.9 29.4 1.3 557 55.5 28.0 0.9 ND ND
1%Pchol.
30:70 ACB
7.1 29.85 1 603 54.7 30.6 0.9 ND ND
1%Pchol.
30:70 ABC
5.8 29.06 1.2 614 57.6 31.0 0.9 152 2.4
1%BFP
30:70 ABC
6.9 30.07 1.3 658 55.2 33.8 0.9 ND ND
1%BFP
SFC

40 35
40:60 NO EMULSIFIER 30:70 NO EMULSIFIER
35 30

30 25

SFC (%)

SFC (%)
25 20

20 15

15 ab 10 ab
abc
abc acb
10 5
10 20 30 40 50 60 10 20 30 40 50 60
Temperature (C) Temperature ( C)
25 50
20:80 NO EMULSIFIER CONTROL
20 40

SFC (%)
SFC (%)

15 30

10 20

5 ab 10
abc
acb
0 0
10 20 30 40 50 60 10 20 30 40 50 60
Temperature (C) Temperature (C)
40
35
30
25
SFC (%)

20
15
10 40-60 abc no E
30-70 abc noE
5
20-80 abc no E
0
10 20 30 40 50 60
Temperature (C)
64
 30 NO EMULSIFIER
1%GMS
25
1%SSL
20 1% PGMS

SFC (%)
1% P-CHOLINE
15 1% BFP
1% GMP
10 1% SMP
1% SMS
5
30:70 ABC 1%E
0
10 20 30 40 50 60
Temperature (C)

30 NO EMULSIFIER
3%SSL
25 3%PGMS
3%P-CHOLINE
20
SFC (%)

3% BFP
15 3%GMP
3%SMP
10 3%SMS

5
30:70 ABC 3%E
0
10 20 30 40 50 60
Temperature (C)
65