MODIFIED STARCHES FOR FOOD AND

BEVERAGE APPLICATION
 TOPICS

 FOOD MODIFIED STARCHES

 Definition
 Native Starch limitations
 Food Modified Starch Advantages
 CHEMICAL MODIFICATIONS
 Crosslinking
 Substitution
 Oxidized
 Thin-boiling
 PHISICAL MODIFICATIONS
 Pre-gelation
 COMBINED MODIFICATIONS
 TOPICS
 CHARACTERIZATION
 Starch Classification
 Characterization Methods
 Microscopic Examination
 Physical Evaluation
 Brabender Amilograph
 Under, Properly, and Over Cooked Starch
 Brookfield Viscosimeter
 Bostwick Consistometer
 Texturometer
 Sensorial Evaluation
 Testing and Evaluation of Pre-gelatinized Starches
 SELECTION GUIDE
 PROMOTING MODIFIED STARCHES
 GUIDE

What is the Function of the Starch

 Gel
 Adhesion
 Hold Water
 Bind  Texture
 Suspend
 Encapsulation  Spoonable
 Texturize
 Fat Sparing (less)  Long
 Thicken
 Film Forming  Cuttable
 Other
 Short
 Other
 GUIDE

Appearance:
Clarity Flavor Intensity:
 Clear and Translucent  Flavor
 Moderately Clear  Delicate
 Cloudy  Hearty (high impact)
 Opaque

Texture
Mouthfeel  Gel
 Creamy  Non-coating
 Coating  Pulpy
 Smooth  Other
 FOOD MODIFIED STARCHES

DEFINITION
Native starch can be altered by different chemical
and/or physical treatments, in order to obtained
different functional capabilities, such as:

– higher or lower gel point

– increased or reduced viscosity
– improve clarity
 FOOD MODIFIED STARCHES

LIMITATIONS OF NATIVE STARCH

• Instability due to retrogradation of amylose

• Cohesive structure

• Breakdown due to high temperature, acid and shear

• Too high viscosity at high concentrations

• Insolubility in cold liquids

• Instability at low temperature (storage condition)

 FOOD MODIFIED STARCHES

NATIVE STARCH GEL

 FOOD MODIFIED STARCHES

FOOD APPLICATION REQUIREMENTS

• Thickening
• Short texture
• Clean taste • Cold water solubility
• Shear resistant • Freeze-thaw stability
• pH resistant • Storage stability of pastes
• Temperature resistant • Film forming (coating)
• Stabilization of emulsions
• Gel formation
 FOOD MODIFIED STARCHES

MODIFIED STARCHES ADVANTAGES

 Impart Stability
 Acid
 Processing (temperature, shear)
 Storage
 Impart Selected Functional Characteristics
 Alter Viscosity
 Alter Viscosity development during Processing
 Improve Film forming properties
 Impart selected Aesthetic properties
 FOOD MODIFIED STARCHES
TRANSLUCID GEL
 CHEMICAL MODIFICATIONS

FDA APPROVED

21 CFR 172.892
 Types of modifications
 Combinations of modifications
 Modification reagents
 Level of modification
 CHEMICAL MODIFICATIONS

CHEMICAL MODIFICATIONS TYPES

Crosslinking
Substitution
Oxidized
Thin-boiling
 CHEMICAL MODIFICATIONS

GENERAL PROCESS
SALT: SWELLING INHIBITOR
CHEMICALS
NaOH: STARCH ACTIVATOR

REACTION
• TIME STARCH
• TEMPERATURE SLURRY
• pH (40% dry solids)
WASHWATER

FILTER DRY
 CHEMICAL MODIFICATIONS

CROSSLINKING
 CHEMICAL MODIFICATIONS // CROSSLINKING

Native Starch Crosslinked Starch

Helices Helices
 CROSSLINKING: OBJECTIVE AND PRINCIPLE

INCREASE STARCH GRANULE STABILITY

AFTER GELATINIZATION

Hydrogen Bonding

Crosslinking
Swollen Starch Granule
 CROSSLINKING

Increases:
 Temperature Stability
 Acid Stability
 Shear Stability

Decreases:
 Viscosity
 Rate of Hydration
 EFFECT OF CROSSLINKING ON STARCH GRANULE

VISCOSITY completely
swollen

X-linked starch

partly retrograded
swollen

native starch
dispersed

native

TIME
95°C 95°C 50°C
CROSSLINKING
 CROSSLINKING

CROSSLINKING EFFECT  WAXY STARCH

Native Low Crosslinking Hi Crosslinking

DIFERENT LEVELS OF CROSSLINKING

pH 5 and 6% Starch
 EFFECT OF CROSSLINKING

 Stabilizes starch granular integrity

 Acid
 Heat/time
 Shear/time
 Alters paste rheology
 Cohesive, short
 Alters viscosity development
 Decreases initial viscosity, stabilizes final viscosity
 CHEMICAL MODIFICATIONS

SUBSTITUTION
 CHEMICAL MODIFICATIONS // SUBSTITUTION

Native Starch Substituted Starch

Helices Helices
 STABILIZATION: OBJECTIVE AND PRINCIPLE

By introducing substitute groups on the starch molecule

the tendency toward intermolecular or inter-branch
association is reduced.
Schematically it is possible to compose the association
between amylase chains with the interlocking between
the rows of teeth of a “zipper”. If one tooth is broken,
then it is not possible to lock the zipper.

Stabilizing Agent

Stabilizing Action

Swollen Starch Granule

 SUBSTITUTION

Increases:
 Freeze/Thaw Stability
 Water Holding Capacity
 Peak Viscosity
 Clarity

Decreases:
 Retrogradation
 Pasting Temperature (Sticky)
 SUBSTITUTION

Temperature
Viscosity

Substituted

Unmodified

Time
SUBSTITUTION
 EFFECT OF STABILIZATION

 Improves starch water-holding ability

 Improves freeze-thaw, cold storage stability
 Decreases retrogradation
 Increases paste clarity
 Improve mouthfeel and “creaminess”
 Lowers starch gelatinization temperature
 Improves ease of cooking
 CHEMICAL MODIFICATIONS

COMBINED MODIFICATION
COMBINED MODIFICATIONS
 CHEMICAL MODIFICATIONS / COMBINED

CROSSLINKING
BENEFITS
OF
BOTH
Synergy Effect
SUBSTITUTION
Properties and Diversification
 COMBINED MODIFICATIONS

Highly Substituted Starches with

Cross
Varying Cross-linking Levels Linking
Level:
Low

Viscosity Medium
[Brabender
Units]
High
Native
Waxy

50ºC 95ºC 50ºC

0 30 60 90

Time [min]
 CHEMICAL MODIFICATIONS

OXIDATION
 OXIDATION

 Sodium hypochlorite
 Depolymerization of polysaccharides
 Oxidation of hydroxyl groups to form carboxyl
groups
 CHEMICAL MODIFICATIONS

THINNING
 CHEMICAL MODIFICATIONS ACID THINNING PURPOSE

 Reduce viscosity

 Weaken granule by cutting

molecular structure

 Use at higher concentration by

reducing viscosity
 Pre-gelatinized Starches

• Description:
– Cold water hydrating, low moisture powdered
products produced by roll drying or spray drying.
• Characteristics:
– Gelled, fluid, or short texture
– Opaque to clear appearance
– Acid, shear, and freeze thaw stability
– Smooth to slightly pulpy texture
 Roll Drying (Drum Drying)

PROCEDURE :
slurry supply
1) Rotating steam heated metal
applicator roll drum (140-180°C).
2) Supply fresh starch slurry to
drum (35% Dry Solids).
3) Slurry gelatinizes to thick
knife paste.
4) Applicator/Rolls apply paste
to drum as thin film.
steam 5) Film dries during rotation.
dried film
6) Knife removes dried film from
drum.
7) Film is milled and sieved.
Alternatives to rolldrying: extrusion (usually results in more
starch degradation thus lower viscosity) or spray drying (less
degradation, cold water swellable)
 Water Swelling (CWS) Starch

• Definition - granular instant starches that swell in

cold systems to develop viscosity
– produced by cooking and spray drying
– produced by slurrying starch in alcohol and subjecting
to high temperature and pressure
• Goal - to achieve intact swollen granules
• Benefit - smooth textured product similar to cook
up
 Cooking + Spray Drying Method (National)

Slurry Jet Cooker

30 - 35% 40 -80 psig
dry solids 300 - 350 ºF
(149-177°C)

310 ºF
154°C

Steam

J. J. Kasica, J. Eden

Dry product
 Thermally Processed Starch

• Extrusion
– Exposed to heat, moisture and shear while under
pressure
– Varying degrees of gelatinization
– Mill to desired particle size
– Benefits:
• Dispersion without lumping
• Minimal dusting
 Heat-Moisture Treatment (Novation)

• Physical treatment in which starches are

treated at varying moisture levels (<35%) for a
certain period of time at a temperature above
the glass transition temperature but below
the gelatinization temperature.
• Decreases susceptibility of starch to acid
hydrolysis for maize
 Pregelatinized Starch
Specific applications:
– Bakery : instant bakery cream, instant pie fillings
– Mayonnaise and salad dressing (cold process)
– Dry mix soups, sauces, gravies
Functionality:
– Instant viscosity development without additional
cooking.
Modified pre-gelled starches:
– Modification should withstand both heat / shear during
roll drying and heat / acid / shear during application.
VARIOUS NATIVE STARCHES AND IMPACT ON FUNCTIONALITY
 SCHEMATIC REPRESENTATION

AMYLOSE AMYLOPECTIN
Mostly linear polymer of A branched polymer of
glucose, connected by glucose, connected by
alpha (1,4) glucosidic alpha (1,4) glucosidic
linkages linkages. The branching
points are alpha (1,6)
glucosidic linkages
 PROPERTIES OF AMYLOSE & AMYLOPECTIN

PROPERTY AMYLOSE AMYLOPECTIN

LINEAR BRANCHED

MOLECULAR VARIES WITH VARIES WITH

WEIGHT STARCH SOURCE STARCH SOURCE
1.0 - 2.5 X 106 200 X 106
“
SOLUBILITY” IN NOT TRULY SOLUBLE
WATER SOLUBLE

GELS TENDS TO RE- STABLE - ONLY

ASSOCIATE - SLIGHT TENDENCY
RETROGRADATION TOWARDS
STIFF RETROGRADATION
NON-GELLING
IODINE COLOR BLUE REDDISH BROWN
 WAYS TO CLASSIFY STARCHES

 According to FDA:
 Native vs. Modified Food Starch (types of modification)
 By Botanical Source:
 Cereal: corn, waxy, rice, wheat
 Tubers: potato
 Roots: tapioca, sweet potato
 Other: banana, sago, pea, bean
 WAYS TO CLASSIFY STARCHES

 By Processing Method:
 Cook-up modified or native
 Pregel modified or native
 Blends of those
 STARCH CHARACTERIZATION

STARCH CHARACTERIZATION METHODS

 MICROSCOPIC EXAMINATION
 PHYSICAL EVALUATION (STARCH PASTES)
 SENSORIAL EVALUATION (STARCH PASTES)
 STARCH CHARACTERIZATION

MICROSCOPIC EXAMINATION
 MICROSCOPIC EXAMINATION

 Identification of Starch Species or Types

 Kofler Gelatinization Temperature
 Iodine Staining (Iodine-Potassium Solution)
 Dye Staining (Methylene Blue)
 IDENTIFICATION OF STARCH SPECIES

Regular Corn Starch Potato Starch Tapioca Starch

Wheat Starch Rice Starch High Amylose Corn Starch

Amplified 1500 X
 STARCH GRANULE PROPERTIES

Size (diameter) Size (diameter)

Starch Type range (µm) average (µm) Shape

Corn Cereal 5 - 25 14 Round, polygonal

Potato Tuber 5 - 100 33 Oval, spherical
Tapioca Root 4 - 35 20 Oval, truncated
Wheat Cereal 2 - 35 15 Round, lenticular
Rice Cereal 3-8 5 Polygonal, angular
Waxy maize Cereal 3 - 25 15 Round, polygonal
Amylomaize Cereal 3 - 24 12 Round, deformed
 RAW STARCH

 Use polarized light

 Observe hilum
 Observe shape
 Observe lost of birefringence
 STARCH GRANUELS MICROSCOPIC VIEW

Amber Light Polarized light

400 X 400 X
 KOFLER GELATINIZATION TEMPERATURE

When starch is heated in an excess of water to

progressively higher temperatures, the granules
hydrate with almost simultaneous loss of their
polarization crosses.

Gelatinization of starch granules in water is detected

by the loss of their polarization crosses (loss of
birefringence)
 STARCH GRANULES POLARIZED LIGHT

5% 50% 95%

62ºC 67ºC 72ºC

 KOFLER GELATINIZATION TEMPERATURE

Not all of the

granules in any
The KOFLER
specie gelatinize at
GELATINIZATION
the same
TEMPERATURE is
temperature, but
defined by a range of
rather over a range
temperature
of about 8 - 10 ºC
 KOFLER GELATINIZATION TEMPERATURE

Kofler Gelatinization
Starch Temperature range (ºC) (*)
Corn 62 - 67 - 72
Potato 58 - 63 - 68
Tapioca 59 - 64 - 69
Wheat 58 - 61 - 64
Rice 68 - 74 - 78
Waxy maize 63 - 68 - 72
Amylomaize 67 - 80 - 92

(*) The recorded temperature correspond to the loss of birefringence by 5, 50 & 95% of the granules
 IODINE STAINING

Waxy starches red color

Non-waxy starches purple - blue color
 IODINE STAINING

Blue-staining corn Red-staining waxy starch

starch
 STARCH CHARACTERIZATION

PHYSICAL EVALUATION
 PHYSICAL EVALUATION STARCH PASTES

 Rheology / Viscosity
 Brabender amylograph
 Brookfield viscometer
 Scott viscosity
 Gel testing
 Bostwick consistometer
 Texturometer TPA
 Syneresis
 Freeze - thaw cycles
 BRABENDER AMYLOGRAPH

The Brabender amylograph is used

to measure the viscosity of a starch
paste. Viscosity is measured during
controlled heating and cooling
cycles at a constant rate of shear.
The resulting amylogram is a
viscosity “fingerprint” of a starch
and allows comparing and predicting
performance of one starch relative to
another.
 BRABENDER AMYLOGRAPH

Scale - linked
to printer

llllllll
Torsion
device

Spindle

Brabender Cup
rotates
^

Heat-at 1.5ºC per minute

 BRABENDER VISCOSITY PROFILE

1200

1000 TEMP (°C )

800

600

400

200

TIME (MINS ) 0 30 60 90 120

TEMP (°C ) 50 95 Hold 95 50 Hold 50
 BRABENDER AMYLOGRAPH

1200
E
1000

A - The pasting or gelatinization 800

temperature is noted when the B C D
600
starch granules begin swelling and
start of measurable viscosity. 400

200 A
B - The peak viscosity provides
an indication of viscosity potential
for the starch. TEMP (°C ) 50 95 Hold 95 50 Hold 50

C - Viscosity upon reaching 95ºC reflects the ease of hydrating the starch granule.

D - Viscosity at the end of a 30-minute hold at 95ºC provides an indication of paste stability.

E - Viscosity after cooling to 50ºC measures re-association or setback that occurs.

 BRABENDER VISCOSITY PROFILE
Torque = 700 cmg
Rotation = 75 rpm
1400 TEMP (oC ) Solids = 6% dry basis
1200 Potato

1000

800 Tapioca
Maize
600 Corn
Rice
400

200 Sago
Wheat

TIME (MINS ) 0 30 60 90 120

TEMP (oC ) 50 95 Hold 95 50 Hold 50
 GETTING THE MOST OUT OF STARCH

Under Cooked
– low viscosity, cloudy, not stable
Properly Cooked
– high viscosity, clear, stable
Over Cooked
– very low viscosity, very clear, cohesive
 MORPHOLOGY OF COOKED STARCH

“Raisin Intact
Granular Like” Partially Partially to ~ Fully Fully Fragments and Colloidal
Partially Swollen Fully Swollen Swollen Swollen Weakening Dispersion
Swollen

5 - 25µ 40µ 50 µ 75 µ 90 µ 100 µ 100 µ

Uncooked (Decreasing refractive Overcooked
index - fragile state)
 EFFECT OF DEGREE OF COOK

Under Cooked Proper Cook Over Cooked

Poor Clarity Clear Clear

Low Viscosity Full Viscosity Low Viscosity

Thin Short & Spoonable Cohesive

Poor Shelf Stability Optimum Stability Poor Stability

Starchy Flavor Clean Flavor Clean Flavor

Birefringent/Incompletely Fully Swollen Granules Fragmented Granules

Swollen Granules
Comparison between Paste Characteristics at Various Degrees of Cook

• Undercooked
• Optimum cooked
• Overcooked

• Compare
– Clarity
– Viscosity
– Cohesiveness
 COOKED PASTE

Optimally Cooked

Overcooked
 BROOKFIELD VISCOSIMETER

Concentric shaft
Concentric cylinders

Liquid under test

Brookfield viscometers have a rotating cylinder or disc coupled, through a torsion spring, to a
constant speed synchronous motor. The spring applies a restoring force to balance the
resistance offered by sample viscosity to spindle rotation. The resulting torque, in centipoises
(cPs), is read directly from a dial.
 BOSTWICK CONSISTOMETER

This instrument is a simple device used to evaluate the

flow characteristics of pureed foods including tomato
purees, marmalades, fruit fillings, pizza sauce, ketchup,
and numerous baby-food products.

Gate

Second
compartment
(graduated)
Compartment
TEXTUROMETER (TEXTURE PROFILE ANALYSIS) JAM TYPICAL CURVE
 STARCH CHARACTERIZATION

SENSORIAL EVALUATION
 SENSORIAL EVALUATION STARCH PASTES

 Clarity (opaque; transparent; cloudy; etc.)

 Color (white; beige; slightly yellow, etc.)
 Aroma / Odor
 Flavor (cereal; normal; starchy; clean, etc.)
 Texture (short; long; gummy; smooth; shiny;
soft gel; cohesiveness; sticky; creamy; brittle;
crispy; elastic; etc.)
 SENSORIAL EVALUATION TEXTURAL TERMS

 Soft gel: Starch paste is easy cut, but if stirred, will smooth out.
 Heavy: Starch paste is thick and has a slow flow. This is typical
of a modified waxy starch.
 Short: Starch paste will be heavy in viscosity. When spooned, it
will drop in large quantities without stringing and with a clean
break.
 Long: Starch paste will have a moderate flow and when
spooned will flow continuously without a break.
 Gummy: Starch paste will be heavy, but when spooned will
string and even snap. This is typical of unmodified starches.
 SENSORIAL EVALUATION TEXTURAL TERMS

 Viscosity in Mouth: the force necessary to move the sample over

the tongue and throughout the mouth.
 Mouth Moating: the thickness of coating in the mouth after tasting,
film sensation on the tongue.
 Rate of Disappearance: the amount of time before the sample has
cleared from the mouth.
 Chalkiness: abrasive mouthfeel or sensation of grittiness /
sandiness on the teeth and tongue.
 Moisture Release: amount of wetness / juiciness released from
food or beverage sample.
 TEXTURE BY STARCH BASE 6.5% SOLIDS

Dent Corn Waxy Maize

fine powder no gel
gelled cohesive paste
opaque very clear
starchy paste less starchy taste
no Frozen/Thaw
stability
features syneresis
 TEXTURE BY STARCH BASE 6.5% SOLIDS

Modified Waxy Maize High Amylose Corn

no gel no viscosity
heavy viscosity insoluble
clarity settling
freeze thaw stability cooked at atmospheric
conditions
 TEXTURE BY STARCH BASE 6.5% SOLIDS

Tapioca Potato
soft gel very clear
cohesiveness no gel
slight opacity salt sensitivity
better stability large starch
clean flavor granule
 TEXTURE BY STARCH BASE 6.5% SOLIDS

Rice
soft gel
cohesiveness
opaque
CHARACTERISTICS OF RAW STARCH 5% COOKED & COOLED

Starch Texture Clarity Flavor

Arrowroot Short Transparent Bland
Maize Short Opaque Cereal
Potato Long Clear Normal
Rice Short Opaque Bland
Tapioca Long Tranparent Bland
Waxy Maize Long Clear Transparent Cereal
Wheat Short Slightly Opaque Cereal
 STARCH CHARACTERIZATION

PREGELS EVALUATION
 PREGELATINIZED STARCH TESTING AND EVALUATION

 Microscopic examination
 Iodine staining
 Water absorption
 Hot and cold viscosity (hydrated)
 Setback (contraction when cooled)
 GRANULATION CHARACTERISTICS INSTANT STARCHES

Parameter Slightly Coarse Fine

Easy of Dispersion Good Fair
Viscosity Development Slow Fast
Breakdown Resistance More Less
Texture Grainy Smooth
Density Lighter Heavier
 SUMMARY

 Starches can be evaluated by multiple classifications.

 Starch function differs with:

 Botanical source

 Modification method

 System in which it is used

 The use of Starch Granule Properties is very important to

helps to predict the finished Texture of Starch.
 KEYS TO STARCH SELECTION

 Selecting a starch for food application requires the

formulator to recognize product demands from
concept to consumer.
 Starch selection and performance depend upon other
ingredients in the formula, targeted product attributes,
processing parameters, distribution, storage, and
market handling demands.
 Early consideration to these key parameters will help
ensure formulation of a high-quality food product.
 FUNCTIONAL FEATURES TO CONSIDER
WHEN CHOOSING A STARCH

1. What product is being made?

2. Physical features of Finished Product?
3. How is product normally manufactured?
4. Can starch be used?
5. What type of starch could be offered to system?
6. What features affect starch?
7. Which starch?
 SELECTION GUIDE

 Formulation requirements
 Product properties  Utilization
 Structural  Ready to Eat
 Aesthetics
 Requires additional
 Organoleptic/Sensory
preparation
 Shelf Stability
 Economics/Maximum Cost
 Product form
 Dry  Legal Status
 Gel
 Pasty
 Semi-moisty
 Liquid
 EFFECT OF OTHER INGREDIENTS

Ingredient Molecule effect Application effect

Disrupts hydrogen bonding Accelerates gelatinization
Acid
Cleaves the starch and viscosity breakdown
Total solids:
Sugar Delay gelatinization and
Salt Compete for available water viscosity development;
Gums Bind water and contribute
Protein to viscosity
Protein May coat the starch granule Delay gelatinization and
Fat and delay hydration viscosity development
Water Required for hydration Balance starch: wáter ratio
IMPACT OF PROCESSING CONDITIONS ON VISCOSITY STABILITY

Equipment Time Degree of Shear

Kettle long low
Swept Surface intermediate moderate->high
Plate Heat Exchanger short high
Jet Cooker
low back pressure short low
high back pressure short high
PDP Positive Displacement Pump short low
Centrifugal Pump short high
Piping variable variable
Emulsification
Colloid mill short high
Homogenization very short very high
 GUIDE

 Packaging and Storage Requirements

 What are the package fill and storage temperature?
 If Frozen
 How quickly
 Storage temperature
 What is the anticipated/desired Shelf Life?
 Reconstitution Requirements
 How is the finished product being reconstituted or used?