applications of modified starch

63. STARCH CONVENTION

Applications

of chemically modified starch

Martin Kozich & Marnik Wastyn

18th of April 2012 Martin Kozich

63. Starch Convention

Starch modification



Confering rheology

Flow ability, elastic/viscous properties, texturizing

Thickening

Stabilizing, viscosity control, long shelf-life stability,

Increase of shear stability, process tolerance

Improvement of pH-stability, acidic stability

Improvement of paste stability

Retrogradation, gelling, amylose crystallisation, freeze-thaw-stability

Film forming properties

Elasticity, cohesion

Adhesiveness – adhesion/cohesion

Binding water

Flocculation

Starch for sensoric properties

Why modification? – To achieve many (new) functionalities !!

Overview - starch properties



Overview - starch products

Starch industry in Germany 2010: 1.94 million t

30%

18%

52%

native starch

modified starch

products fromsaccharification

www.staerkeverband.de



Starches for food application

Chemically modified starches are used, because they provide

functional attributes in food applications that native starches

normally cannot provide

Heat resistance

Acid resistance

Shear resistance

Improved freeze-thaw-stability

native starches

physically modified starches

chemically modified starches

Starches for food application

Properties of chemical modified starches depends on

Raw material: maize, potato, wheat, tapioca, rice,…

Type of modification: ether, ester, cross-linking,..

Degree of modification



Chemically modified starches for food

E - NUMBER CHEMICALLY MODIFIED STARCH

E 1404 Oxidised starch

E 1410 / E 1412 Monostarch phosphate / distarch phosphate

E 1413 Phosphated distarch phosphate

E 1414 Acetylated distarch phosphate

E 1420 Acetylated starch

E 1422 Acetylated distarch adipate

E 1440 Hydroxy propyl starch

E 1442 Hydroxy propyl distarch phosphate

E 1450 / E 1452 Starch sodium octenyl succinate / Al-type

E 1451 Acetylated oxidised starch

For Europe, chemically modified starches classified by E-number

For USA, classified by FDA Code of Federal Regulations 170.3

Chemical modification is restricted by legislation!



Derivatisation

Increase of binding water, swelling power

and viscosity

Repression of retrogradation

Increase of freeze-thaw-stability

Increase of baking stability

Cross-linked starches

Increase of process tolerance for heat,

acid & shear resistance

Alteration of texture to short structure,

creamy

Chemically modified starches



Chemically modified starches

Cross-linked starches Derivatisation

For example:

Acetylated distarch adipate (E 1422)

Hydroxy propyl distarch phosphate (E 1442)

EXAMPLES for APPLICATIONS:

Dairy products

Chilled and frozen products: to

deliver required shelf-life

Fruit-preparations: yoghurts,

desserts, ice creams,…

Salad dressings and mayonnaise

Bakery,…..



Properties of chemically modified starches

Incre

asin

g e

as

e o

f co

okin

g

Increasing freeze-thaw stability

Incre

asin

g h

eat, a

cid

an

d s

hear re

sis

tan

ce

Low Crosslinking

Low Stabilization

Low Crosslinking

High Stabilization

High Crosslinking

Low Stabilization

High Crosslinking

High Stabilization

Starch, Structure and Functionality, by P.J. Frazier et al. (1997)



Overview about non-food applications

Paper industry

Wet end, surface, coating, spray…

Adhesives

Corrugated board

Lamination, tissue, book-binding

Remoistable adhesives

Paper bags

Wallpaper glue, glues for posters

Textile market

Sizing, textile printing, glass fiber, finishing,…

Construction sector

Tile cement, plaster, stucco

Shotcrete, self compacting concrete

Emulsion paints, renders



Overview about non-food applications

Oil drilling industry

Flocculation - refractories

Waste water treatment

Foundry

Mining industry

Ore flotation

Ore sedimentation

Starches for pharmaceutical use

Plasma volume expander

For immediate release formulation in tablets

Starches for cosmetics

Lotions, different creams for sun, baby, lid shadow,…

Agrochemicals: controlled release, seed coatings

Thermoplastic starches



Selected examples for non-food applications

Adhesives

Paper bags

Paper industry

Wet end

Textile market

Sizing

Construction sector

Tile cement



Chemically modified starches for paper

Starches for

paper industry Modification Rate Application

Wet end starch cationic

(amphoteric) 21%

drainage, sizing, retention, dry

strength

Surface usually enzymatic,

oxidised 64%

printability, smoothness, Z-

strength, breaking length,

bursting strength, stiffness

Coating oxidised, dextrins;

enzymatic 12%

co-binder, printability, water

retention

Spray native; cross-linked 3% plybond strength




Schematic of a

paper machine

Doctoral thesis about paper

production;

J. Gattermayer (2001)

WET END STARCHES – WHY CATIONIC STARCHES ?

Native starches only for system with low conductivity

Cationic starches: overcome electrostatic forces




PROPERTIES OF WET END STARCHES

• Increase of hydrogen bonds between fibers

Dry strenght additive

• Increase of filler retention due to ionic character Retention aid

• Protective colloid for ASA emulsification Sizing

• Increase of dry substance in the press section of the paper machine Drainage



Chemically modified starches for adhesives

Starches for paperbag glueing Corn or potato starch

Cross-linked cold water swellable starches

Glue preparation with dissolver

starch conc. from 17% to 40%

Transversal, longitudinal and bottom gluing

Glue preparation with a dissolver




Starches for paperbag gluing Advantages of chem. mod. starches

High tack

Minimal splashing

Excellent viscosity stability

Excellent runability

Wheel gluing unit

Bottom gluing




PRINCIPLES ABOUT WORKABILITY OF STARCHES

for paperbag gluing – why crosslinking?




PRINCIPLES ABOUT WORKABILITY OF STARCHES

for paperbag gluing – why crosslinking?

high splashing no splashing



Chemically modified starches for sizing

SIZING: sizing of warp yarn is essential to reduce breakage of the yarn and protect

the warp yarn during weaving on the machine.

Starches mostly used to facilitate textile treatment and are removed after process.

Sizing agents: degraded modified starch ether/ester based on potato / tapioca

• Preferred chem. modification: hydroxypropyl, carboxymethyl, acetyl, carbamate

Raw fiber

Sizing of fiber

Requirements of sizing agents

High adhesive property to yarns

Reduction of roughness of yarns (hairy)

Better slipping / scrub resistance

High elongation of coated yarns

High tensile strength

Good desizing properties / solubility




Investigation of starch films – test for tensile strength / elongation

native potato starch

native corn starch

hp-ox potato starch ox potato starch




Determination of desizability – remaining starch by iodine test

Sized textile

Partly desized (not modified)

Scale of purple

Completely desized (modified)



Chemically modified starches for dry mortar

Starch application in dry mix mortar

Plaster & render

Tile adhesives

• Highly substituted starch ether

• Hydroxypropyl / carboxymethyl

• Dosage: < 0.2% / mortar

• Potato, maize & waxy types

• Used in combination with celluloseether




Chemically modified starches for tile cement

There is no correlation of starch ether between aqueous viscosity and

thickening effect in dry mortar!

Why chem. modified starch? - The behaviour of starch is strongly

dosage-dependent: it acts as a thickener when the incorporated dosage

is up to 0.2% of weight. The thickening effect takes place because

starch is adsorbed onto inorganic particles acting as a flocculant to

make a network, as confirmed by zeta-potential and particle size

distribution results.

Aqueous viscosity Slump flow

J.I.Álvarez et al. Carbohyr. Polym. 80, 222 (2010)

A. Glatthor, Schleibinger Rheologie-Kolloquium Regensburg, 2005




Impact of chemically modified starches for tile cement Thickening effect

High impact on rheology (yield point)

Optimal wetability & workability

Adjust open time

Setting time & retarded setting

Optimale tensile adhesive strength

Slip resistance

Typ A: highly modified starch Typ B: unmodified starch

Slip resistance

Typ A Typ B

Open time



Applications of chemically modified starch

Thank you for your attention Marnik Wastyn Martin Kozich

applications of modified starch

Documents

modified starch e

starch convention starches

acetylated starch e

modified starches starches

oxidised starch e

starch convention properties

starch convention applications

hydroxy propyl starch