Modulation of the thermomechanical properties

of fats using surfactants

Alejandro Marangoni1, Nuria Acevedo1,2

1Department of Food Science University of Guelph

2Department of Food Science Iowa State University

2

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

Acevedo and Marangoni, Crystal Growth and Design, 2010a

d

Tuning fork

Molecule

Sn-2

Sn-1 Sn-3

Can we “deliver” improved functionality of fat by modifying the

properties of the nanoscale?

3

4

roll-in shortening

The shortening

5

16 18 20 22 24 26 28 30 32 34

0.46 nm

0.39 nm

2

Inte

nsity

, au

0.37 nm

6

Fatty Acid APPS Our

shortening

GMP GMS BFP

14:00 0.20 0 1.25 0 0

16:00 12.35 11.08 57.39 11.16 11.50

16:1c9 0.07 0 0 0 0

17:00 0.18 0.12 0 0.25 0.30

18:00 18.20 25.75 38.21 87.57 86.40

18:1t4 0.02 0 0 0 0

18:1t5 0.27 0 0 0 0

18:1t6-8 0.48 0.09 0.12 0 0.03

18:1t9 3.37 0.13 0.24 0 0.05

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

18:2c9-t12 1.61 0.41 0 0 0

18:2t9c12 1.29 0.33 0 0 0

18:2n6 6.92 35.32 0.25 0 0.06

18:2c9c15 0.87 0 0 0 0

Fatty Acid APPS Our

shortening

GMP GMS BFP

20:00 0.42 0.28 0.50 0.58 0.58

18:3n6 0 0.15 0 0 0

20:1c11 0 0 0 0 0

18:3n3 0.31 4.88 0 0 0

18:2tt CLA 0 1.06 0 0 0

22:00 0.33 0.24 0 0.33 0.3

24:00 0 1.21 0 0 0

22:5n3 0 1.46 0 0 0

Trans fat

content 29.20 3.70 1.18 0 0.50

7

8

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 75 BFP

Mono and Di Glycerides from hydrogenated palm fat

9

Crystallization in a votator

SAMPLE AB

SAMPLE ABC SAMPLE ACB

UNIT A

-2oC

UNIT B

15oC

UNIT C

10oC

PUMP VESSEL

VOTATOR LINE

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)

2. SSL (Sodium Stearoyl Lactylate)

3. SMS (Sorbitan Monostearate)

4. PGMS (Polyethylene Glycol

Sorbitan Monostearate)

5. P-CHOLINE (Phosphatidylcholine)

6. BFP (Mono and Di Glycerides from hydrogenated palm fat)

7. SMP (Sorbitan Monopalmitate)

8. GMP (Glyceryl Monopalmitate)

75 SAMPLES

ANALYSIS

CONTROL: HIGH SATURATED AND TRANS FAT

ROLL- IN SHORTENING

A and C: scraped surface chillers

B: working unit

MATERIALS AND METHODS

ANALYSIS

Differential Scanning Calorimetry (DSC)

Physical Properties

Thermal Properties

Microstructure

Nanostructure

Rheological Properties

Solid Fat Content (SFC )

Oil Binding Capacity (OMG)

Small Deformation Tests

Powder X-ray Diffraction (SAXD, WAXD)

Cryo-TEM

Polarized Light Microscopy (PLM)

10

11

10 20 30 40 50 6010

15

20

25

30

35

40

ab

abc

40:60 NO EMULSIFIER

Temperature (C)

SF

C (

%)

10 20 30 40 50 600

5

10

15

20

25

abcab

acb

20:80 NO EMULSIFIER

Temperature (C)

SF

C (

%)

10 20 30 40 50 600

5

10

15

20

25

30

35

40

40-60 abc no E30-70 abc noE

20-80 abc no E

Temperature (C)

SF

C (

%)

10 20 30 40 50 605

10

15

20

25

30

35

abcab

acb

30:70 NO EMULSIFIER

Temperature (C)

SF

C (

%)

10 20 30 40 50 600

10

20

30

40

50CONTROL

Temperature (C)S

FC

(%

)

SFC

12

10 20 30 40 50 600

5

10

15

20

25

30 NO EMULSIFIER

1%GMS

1%SSL

1% SMS

1% PGMS

1% P-CHOLINE

1% BFP

1% SMP1% GMP

30:70 ABC 1%E

Temperature (C)

SF

C (

%)

10 20 30 40 50 600

5

10

15

20

25

30 NO EMULSIFIER

3%SSL

3%SMS

3%PGMS

3%P-CHOLINE

3% BFP

3%SMP

3%GMP

30:70 ABC 3%E

Temperature (C)

SF

C (

%)

13

FHSO:SO PROPORTION

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

3%SSL AB 45.4

3%SSL ABC 30.5 19.8 9.8

3%SSL ACB 41.7 33.5 11.8

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

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

3%GMP ABC 28.3

3%GMP ACB 7.3

OIL MIGRATION (%) SHORTENING

CONTROL

2.8 %

OIL BINDING

14

RHEOLOGICAL PROPERTIES

NO

EM

ULS

IFIE

R

1%G

MS

1% S

SL

3% S

SL

1% P

GM

S

3%

PG

MS

1%

P-C

HO

LINE

3% P

-CH

OLI

NE

1% B

FP3%

BFP

1% G

MP

3%

GM

P1%

SM

P

3%

SM

P1%

SM

S3%

SM

S

NO

EM

ULS

IFIE

R1%

GM

S1%

SSL

3% S

SL

1% P

GM

S

3% P

GM

S

1% P

-CH

OLI

NE

3% P

-CH

OLI

NE

1% B

FP3%

BFP

1% G

MP

3%

GM

P1%

SM

P3%

SM

PC

ontrol

0.0

0.5

1.0

1.5

2.030:70ABC ACB

G' (M

Pa)

Control Control

GMS

P-CHOLINE

BFP

GMP

1% P-CHOLINE

BFP 1%

NO

EM

ULSIF

IER

1%

GM

S1%

SSL

3% S

SL

1% P

GM

S

3%

PG

MS

1%

P-C

HO

LIN

E

3% P

-CH

OLIN

E1%

BFP

3% B

FP

1% G

MP

3%

GM

P1%

SM

P 3

% S

MP

1% S

MS

3% S

MS

NO

EM

ULSIF

IER

1%G

MS

1% S

SL

3% S

SL

1% P

GM

S

3% P

GM

S

1% P

-CH

OLIN

E

3% P

-CH

OLIN

E1%

BFP

3% B

FP

1% G

MP

3%

GM

P1%

SM

P3%

SM

PC

ontr

ol

0

300

600

900

1200

1500 30:70ABC ACB

*

(Pa)

RHEOLOGICAL PROPERTIES

Control BFP

GMP 1% Control

GMS

GMP 1%

16

MICROSTRUCTURE (PLM)

100µm

Control Fat blend

< Control

GMP Eq. Diam

Fat blends

Control

Equivalent

Diameter

2.35 0.51 m

NO

EM

ULS

IFIE

R

1%G

MS

1% S

SL

3% S

SL

1% P

GM

S

3% P

GM

S

1% P

-CHO

LINE

3% P

-CHO

LINE

1% B

FP3%

BFP

1% G

MP

3% G

MP

1% S

MP

3% S

MP

1% S

MS

3% S

MS

NO

EM

ULS

IFIE

R1%

GM

S1%

SSL

3%

SSL

1% P

GM

S

3% P

GM

S

1% P

-CHO

LINE

3% P

-CHO

LINE

1% B

FP3%

BFP

1% G

MP

3% G

MP

1% S

MP

3% S

MP

Con

trol

0.0

0.5

1.0

1.5

2.0

2.530:70ABC ACB

Eq

uiv

ale

nt

Dia

mete

r (

m)

17

40-6

0 ab

40-6

0 ab

c

30-7

0 ab

30-7

0 ab

c

30-7

0 ac

b

20-8

0 ab

20-8

0 ab

c

20-8

0 ac

b

10-9

0 ac

b

CONTR

OL

0.0

0.5

1.0

1.5

2.0

2.5NO EMULSIFIER

Eq

uiv

ale

nt

Dia

mete

r (

m)

ab 1

% G

MS

ab 1

% S

SL

ab 3

% S

SL

abc

1% G

MS

abc

3% G

MS

abc

1% S

SL

abc

3% S

SL

acb N

O E

MULS

IFIE

R

acb 1

% G

MS

acb

3%

GM

S

acb 1

% S

SL

acb 3

% S

SL

CONTR

OL

0.0

0.5

1.0

1.5

2.0

2.510:90

Eq

uiv

ale

nt

Dia

mete

r (

m)

PLM

NO E

MULS

IFIE

R

1%GM

S

3%GM

S

1% S

SL

1%PGM

S

1% S

MS

3% S

MS

Contr

ol0.0

0.5

1.0

1.5

2.0

2.520:80 abc

Eq

uiv

ale

nt

Dia

mete

r (

m)

NO E

MULS

IFIE

R

1%GM

S

3%GM

S

1% S

SL

3% S

SL

3%PGM

S

1% S

MS

3% S

MS

Contr

ol0.0

0.5

1.0

1.5

2.0

2.520:80 acb

Eq

uiv

ale

nt

Dia

mete

r (

m)

18

NANOSTRUCTURE

SHORTENING

CONTROL

FHSO:SO

NO

EM

ULS

IFIE

R

1%G

MS

1% S

SL

1% P

GM

S1%

BFP

1% G

MP

1% S

MP

1%

SM

S

AB N

O E

MULS

IFIE

R

AB 3

%G

MS

ABC N

O E

MULS

IFIE

R

ACB N

O E

MULS

IFIE

R

ACB 1

%G

MS

CO

NTRO

L

0

50

100

150

200

25030:70 20:80ABC

Nan

o-e

qu

ivale

nt

Dia

m.

(nm

)

19

SAXRD

NO

EM

ULSIF

IER

1%

GM

S1%

SSL

3% S

SL

1% P

GM

S

3% P

GM

S

1%

P-C

HO

LIN

E

3% P

-CH

OLIN

E1%

BFP

3% B

FP

1% G

MP

3% G

MP

1% S

MP

3% S

MP

1% S

MS

3%

SM

S

NO

EM

ULSIF

IER

1%

GM

S

3%G

MS

1% S

SL

3% S

SL

1%PG

MS

3%PG

MS

1% S

MS

3% S

MS

CO

NTR

OL

0

50

100

150

200

250

300

35020:8030:70 ABC

Do

main

Siz

e (

Å)

NANOSTRUCTURE

Cryo-TEM

< Control Fat blends

Control

GMS

PGMS

BFP

GMP

SMS

1% Eq. Diam.

Length/With ratio

Control = 4

Fat blends = 2.5 – 3.5

Fat blends

Physical Properties Rheological

Properties

Thermal Properties Microstructure Nanostructure

OMG

(%)

SFC 20C

(%)

G’ (MPa) * (Pa) Tm

(C)

Hm

(J/g)

Eq.D

(µm)

EqD

(nm)

L/W

ratio

Polymorphic

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

1%GMS 2.9 28.66 1.7 1010 60.6 57.9 1.1 155 3.3

30:70 ACB

1%GMS 2.6 29.76 2.1 1292 61.0 58.7 1.1 105 3

30:70 ABC

1%GMP 3.1 30.84 1.8 891 56.4 34.39 1.3 180 2.4

30:70 ACB

1%GMP 3.8 30.24 1.9 789 55.0 35.5 1.6 ND ND

30:70 ABC

1%Pchol. 7.9 29.4 1.3 557 55.5 28.0 0.9 ND ND

30:70 ACB

1%Pchol. 7.1 29.85 1 603 54.7 30.6 0.9 ND ND

30:70 ABC

1%BFP 5.8 29.06 1.2 614 57.6 31.0 0.9 152 2.4

30:70 ABC

1%BFP 6.9 30.07 1.3 658 55.2 33.8 0.9 ND ND

21

Diffusion Coefficient, D (x 10-12 m2/s) OMG(%)

number

name @ 4 °C @ 18 °C @ 20°C

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

Mechanism?

22

Case 1 limited amount of emulsifiers is miscible in fat system. The small

amounts of emulsifiers act as impurities and result in imperfections of fat crystals. It

will promote or retard polymorphic transformation of fat crystals.

Case 2 fats and emulsifiersare highly miscible. In this case, fats-emulsifiers

binary phase shows miscible phase behavior or molecular compound formation.

Case 3 fats and emulsifiers are totally imiscible in a soild state. In nucleation,

emulsifiers may work as seeds of fat crystals under special conditions, foe example, a

template film. In crystal growth, the emulsifiers are adsorbed at steps or kninks of fat

crystals at crystal-liquid interfaces and inhibit crystal growth and thereby modify

crystal morphology.

Case 4 emulsion systems; emulsifiers may induce fat emulsifiers interaction.

Acceleration of nucleation may occur at the interface of the emulsion onto which the

adsorbed hydrophilic emulsifiers become templetes for heteroginious nucleation.

Garti, 2002, FOOD EMULSIFIERS:STRUCTURE-REACTIVITY RELATIONSHIPS, DESIGN AND APPLICATIONS. In Physical Properties of Lipids, Marcel Dekker Inc. , NY

Entropy-driven functionalization of the melting behavior of fats

23

mm

m P

HT

S

24

25

26

Average of the 63 enthalpies of melting = 30.7 kJ/mol

27 Temperatures normalized to 37oC

28

29

Entropy, not Enthalpy

30

Statistical Thermodynamic Proposal

31

32

Isolated System? NVT ensemble

Microcanonical Ensemble = Statistical Ensemble of Isolated Systems

33

Microscopic World

34

lnBS k W

!

!( )!

nW

k n k

S is the configurational entropy for mixing k imperfections into n lattice sites. W is the number of combinations of k in n, where order is not important.

22 1 2 1

1

ln ln ln SS S B S B S B

S

WS S k W k W k

W

35

1SSSW

For a perfect (GMP) crystal without impurities, k=0 and W=1

!

!( )!

nW

k n k

lnSSS impurity SSS B SSS impurityS S k W

and thus:

Macroscopic World - melting

36

mm

m

HS

T

m L SS S S

,1 ,2 1 1 2 2

2 1 1 2

( ) ( )

( ) ( )

m m L S L S

S S L L

S S S S S S

S S S S

Macro-micro proposal

37

, ,lnSSS GMP SSS SSS GMP m SSS m SSS GMPS S R W S S

, ,ln

m SSS m SSS GMP

SSS GMP

S SW

R

Can we control epitaxial stacking of lamellae using surfactants?

38

Can we make 2D van der Waals heterostructures?

39

Engineering epitaxial stacking using surfactants via modulation of surface energy

40

How?

• By control of surface nucleation……

• Compares favourably with Lifshitz model

41

(001) 2

[001] 38.5 /2

f

f M

H dT mJ m

T V

3

2

22 2

2

n 1ε 13 3hνA kT

4 ε 1 16 2 n 1

SSSS

SS

2 2/ 24 (0.165 ) 35.0 /SS SSA nm mJ m

42

Nice Lift!

43

Funding Agencies

Natural Sciences and Engineering Research Council

Canada Research Chairs Program

Ontario Ministry of Agriculture and Food

Coasun Inc.

Thank You!

Thank You!