RHEOLOGICAL MODELLING

OF BIOPOLYMER
Presented by:
N SAI PRASANNA
Roll No.: 17AG63R20

Agricultural and Food Engineering Department

IIT Kharagpur
 CONTENTS
 INTRODUCTION
 CLASSIFICATION
 OBJECTIVES SELECTED
 CASE STUDY
- OBJECTIVES
- MATERIALS AND METHODS
- RESULTS AND DISCUSSION
- CONCLUSION
 REFERENCES
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 BIOPOLYMERS: INTRODUCTION
• The term “biopolymers” usually describes
polymers produced in a natural way by
living species.
• Their molecular backbones are composed
of repeating units of saccharides, nucleic
acids, proteins or amino acids and
sometimes various additional chemical
side chains contributing also to their
functionalities.
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 BIOPOLYMERS: INTRODUCTION
Biopolymers fall into two principal categories
• Polymers that are produced by biological systems such
as microorganisms, plants and animals. (bio-degrade
with the action of micro-organisms, heat and moisture).
• Polymers that are synthesized chemically but are
derived from biological starting materials such as
amino acids, sugars, natural fats and oils.
• NOTE: Biopolymers can be made using waste starch
from a crop that has been grown for food use.
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CLASSIFICATION OF BIOPOLYMERS

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Biopolymers found in nature & their functions

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The following properties are more
intensively studied.
A) Polymer density (ρ, in g/cc).
B) Tensile properties 1. Tensile strength (s, in MPa)
2. Tensile modulus (E, in GPa)
3. Ultimate strain (є, in %).
C) Specific tensile properties are obtained by dividing
(The original properties by the polymer density)
1. Specific tensile strength (s*, in Nm/g)
2. Specific tensile modulus (E*, in kNm/g).
D) Characteristic temperatures
1. Glass transition temperature ( in °C)
2. Melting point ( in °C).
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 Films preparation
 Film characterization

(Moisture Determination, Impedance Spectroscopy(IS),

(TGA), (DSC) and Water vapour transmission)
 Mechanical tests (Tensile strength & percentage elongation)
 Effects of temperature and plastizicer concentration on
rheological properties of starch solutions
 To study and verify the flow behaviour (shear stress against
shear rate) by fitting to various rheological models
 To study the variation of the consistency coefficient with both
temperature and placticizer concentration
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CASE STUDY
Title: Influence of glycerol and temperature on
the rheological properties of potato starch
solutions
Authors:
German Ayala
Ruben A. Vargas
Ana C. Agudelo
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CASE STUDY

OBJECTIVES:
 Effects of temperature and glycerol concentration on
rheological properties of potato starch solutions were
investigated.
 To study and verify the flow behaviour (shear stress
against shear rate) by fitting to various models.
 To study the variation of the consistency coefficient
with both temperature and glycerol concentration.
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 BACKGROUND…
 In cold water, starch is non-soluble, but when starch
solutions are heated above the gelatinization
temperature, the viscosity increases due to starch
granules losing their crystallinity and absorb large
amounts of water.
 An important step of manufacturing process of films
based on starches is the control of the rheological
properties of the filmogenic solutions, where the
apparent viscosity of starch solutions can be modified
by temperature, shear rate, plasticiser type and
combinations of these variables.
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MATERIALS AND METHODS
Potato starch preparation:

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Edible films preparation (casting process)
*3gm of PS were initially gelatinized in 100 ml of distilled
water at 85±1°C for 15 min under constant agitation with
magnetic stirring at 250 r.p.s.
*After 15 min, a viscous and transparent solution was
obtained.
*Glycerol was then added in different proportions into
identical starch solutions in beakers at 85±1°C and mixed
for 15 min under constant agitation at 250 r.p.s.
*We prepared three glycerol/potato starch concentrations
with weight fraction G/PS = 0.1, 0.3 and 0.5 respectively.
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 MATERIALS AND METHODS
RHELOGICAL ANALYSIS:(Brookfield viscometer)
 The shear stress(τ) was measured as a function of shear
rate which was increased from 0.02 to 0.33(per sec)
using a spindle type S-62.
 All analyses (rheological properties of G/PS solutions)
were performed at least three times using the Brookfield
viscometer between 20-80% full torque scales at
temperatures (30, 40, 50 and 60°C).
 Data were analysed using MS-Excel software.
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Shear stress as a function of shear rate for the
G/PS solutions were fitted to different models
Power law model

Herschel-Bulkley model

Bingham model

Modified Bingham model

Casson model
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 RESULTS AND DISCUSSION

Viscosity vs. shear rate in double Flow curves in double logarithmic scale at
logarthemic scale for G/PS = 0.1 solution 30°C for G/PS = 0.1, 0.2 and 0.3.
at different temperatures 10/21/2021 16
Parameters of different models for flow behaviour
at different G/PS concentrations and temperatures

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 CONTINUATION….

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 CONTINUATION….

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Fitting parameters τ₀, K and n from Herschel-Bulkley model for
Temp(°C Parameter Equation
G/PS solutions at different )
Glycerol concentrations (C) 30 τ₀ (Pa) τ₀ = -0.85C² + 0.63C -
and temperatures K (Pa sⁿ) 0.03
n K = 2.00C² - 2.35C + 1.08
n = 1.17C² - 0.44C + 0.48
40 τ₀ (Pa) τ₀ = -0.82C² + 0.63 - 0.03
K (Pa sⁿ) K = 3.14C² - 3.12C + 1.14
n n = 0.21C²+ 0.08C + 0.48
50 τ₀ (Pa) τ₀ = -1.04C² + 0.74 - 0.04
K (Pa sⁿ) K = 3.45C² - 3.34C + 1.40
n n = 0.1C² + 0.19C + 0.49
60 τ₀ (Pa) τ₀= -0.75C² + 0.60 - 0.03
K (Pa sⁿ) K = 3.37C² - 3.25C + 1.09
n n = 2.22C² - 0.74C + 0.59
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Empirical equation from Herschel-Bulkley model for
shear stress prediction as a function of glycerol
concentration and the shear rate at different isotherms

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Empirical model obtained from the Herschel-Bulkley equation for the
prediction of shear stress as a function of
shear rate and glycerol
concentration in G/PS
solutions at 40°C

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A single equation combining effects of temperature and
glycerol concentration on shear stress is proposed.
 The shear stress values were fitted by multiple linear
regressions to the following expression:

T is the absolute temperature, β₀, β₁, β₂, β₃, β₄, β₅ are

constants.
 β₀ is the mean of all shear stress values
 β₁, β₂ are related to the linear effect due to temperature and
glycerol concentration, respectively
 β₃, β₄ are related to second power effects due to same
variables
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Combined effects of temperature and glycerol concentration
on the shear stress for G/PS solution at: a – 0.20, b – 0.10,
and c – 0.05 r.p.s.

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DEPENDENCE OF CONSISTENCY COEEFICIENT
 The K values reported in Table 1 obtained by fits to Herschel Bulkley
model were fitted to equation given by (Velez and Barbosa (1997))
 Dependence of ln K on both the temperature (T) and glycerol content
(G/PS) in the solutions
shown in the model below.

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 CONCLUSIONS
1. Experimental results show that the rheological
properties of G/PS solutions are controlled by the
temperature and glycerol content in the solutions within
the temperature range of 20-60°C and glycerol/potato
starch weight fraction from 0 to 0.5.
2. It was found that the Herschel-Bulkley model is most
appropriate equation for describing rheological behaviour
of G/PS solutions as a function of glycerol concentrations
and temperature. (n=0.44 & 0.78 typical of pseudoplastic
fluids). 10/21/2021 26
3. The dependence of the consistency coefficient(K) on
both the glycerol concentration and temperature was well
described by an exponential expression with an activation
energy value of 2.78 KJ/mol which indicates the energy
necessary to induce movement in the G/PS solutions
4.This study demonstrates new findings related to the
rheological properties in glycerol/ potato starch solutions
and could serve for future works in the simulation and
design of industrial equipment.

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 REFERENCES
 Velez J.F. and Barbosa G.V., (1997). Effect of concentration
and temperature on the rheology of concentrated milk,
Journal of American Society of Association Executives, 40,
1113-1117.
 Velde K.V.D. and P. Kiekens. P., (2002).Biopolymers:
overview of several properties and consequences on their
applications, International journal on Polymers, 21, 433–442.
 Ayala G., Agudelo A., and Vargas R., (2012a). Effect of
glycerol on the electrical properties and phase behavior of
cassava starch biopolymers, DYNA, 79, 138-147.
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 REFERENCES
Ayala G.V., Agudelo A.C.H., and Vargas R.A.Z., (2012b).
Comparative study and characterization of starches isolated from
unconventional tuber sources. Journal of Polymer Engineering, 32, 531-
537.
Ayala G.V., Agudelo A.C.H., and Vargas R.A.Z., (2013). Effect of
glycerol concentration and temperature on the rheological properties of
cassava starch solutions. Journal of Polymer Enggineering, 33, 141-148.
Ayala G.V., Agudelo A.C.H., and Vargas R.A.Z., (2014). Influence of
glycerol and temperature on the rheological properties of potato starch
solutions, International Journal of Agrophysics, 2014, 28, 261-268.
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10/21/2021 30
in addition to water, the most commonly used plasticizers are polyols, mono-, di-
and oligosaccharides. Polyols have been found to be particularly effective for use
in plasticized hydrophilic polymers Glycerol (GLY) was, thus, nearly
systematically incorporated in most of the hydrocolloid films GLY is indeed a
highly hygroscopic molecule generally added to film-forming solutions to prevent
film brittleness.
Recently, many studies have focused on the use of polyols such as GLY ],
ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG),
tetraethylene glycol and polyethylene glycol (PEG), propylene glycol (PG) ,
sorbitol, mannitol and xylitol; fatty acids; monosaccharides (glucose, mannose,
fructose, sucrose) ethanolamine (EA) urea; triethanolamine (TEA) ; vegetable
oils; lecithin; waxes amino acids  surfactants and water  as plasticizers of edible
and/or biodegradable films.

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