Applications of chemically modified starch

63. STARCH CONVENTION

Martin Kozich & Marnik Wastyn

Starch modification

18th of April 2012

63. Starch Convention

Martin Kozich

Overview - starch properties

Why modification? To achieve many (new) functionalities !!
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
63. Starch Convention Martin Kozich

18th of April 2012

Overview - starch products

Starch industry in Germany 2010: 1.94 million t

30%

52%

18%

native starch modified starch www.staerkeverband.de

products from saccharification

18th of April 2012

63. Starch Convention

Martin Kozich

Starches for food application

native starches physically modified starches chemically modified starches

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

Properties of chemical modified starches depends on

Raw material: maize, potato, wheat, tapioca, rice, Type of modification: ether, ester, cross-linking,.. Degree of modification
18th of April 2012 63. Starch Convention Martin Kozich

Chemically modified starches for food

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!

E - NUMBER E 1404 E 1410 / E 1412 E 1413 E 1414 E 1420 E 1422 E 1440 E 1442 E 1450 / E 1452 E 1451
18th of April 2012

CHEMICALLY MODIFIED STARCH Oxidised starch Monostarch phosphate / distarch phosphate Phosphated distarch phosphate Acetylated distarch phosphate Acetylated starch Acetylated distarch adipate Hydroxy propyl starch Hydroxy propyl distarch phosphate Starch sodium octenyl succinate / Al-type Acetylated oxidised starch
63. Starch Convention Martin Kozich

Chemically modified starches

Cross-linked starches
Increase of process tolerance for heat, acid & shear resistance Alteration of texture to short structure, creamy

Derivatisation
Increase of binding water, swelling power and viscosity

Repression of retrogradation
Increase of freeze-thaw-stability Increase of baking stability

18th of April 2012

63. Starch Convention

Martin Kozich

Chemically modified starches

Cross-linked starches Derivatisation

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,..

For example: Acetylated distarch adipate (E 1422) Hydroxy propyl distarch phosphate (E 1442)
18th of April 2012 63. Starch Convention Martin Kozich

Properties of chemically modified starches

Increasing heat, acid and shear resistance

Increasing ease of cooking

Low Crosslinking Low Stabilization

Low Crosslinking High Stabilization

High Crosslinking Low Stabilization

High Crosslinking High Stabilization

Increasing freeze-thaw stability

Starch, Structure and Functionality, by P.J. Frazier et al. (1997)
18th of April 2012 63. Starch Convention Martin Kozich

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
18th of April 2012 63. Starch Convention Martin Kozich

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
18th of April 2012 63. Starch Convention Martin Kozich

Selected examples for non-food applications

Paper industry
Wet end

Textile market
Sizing

Adhesives
Paper bags

Construction sector
Tile cement

18th of April 2012

63. Starch Convention

Martin Kozich

Chemically modified starches for paper

Starches for paper industry Wet end starch

Modification

Rate 21%

Application

cationic (amphoteric)
usually enzymatic, oxidised oxidised, dextrins; enzymatic native; cross-linked

drainage, sizing, retention, dry strength

printability, smoothness, Zstrength, breaking length, bursting strength, stiffness co-binder, printability, water retention plybond strength
Martin Kozich

Surface

64%

Coating Spray
18th of April 2012

12% 3%

63. Starch Convention

Chemically modified starches for paper

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
18th of April 2012 63. Starch Convention Martin Kozich

Chemically modified starches for paper

PROPERTIES OF WET END STARCHES

Dry strenght additive

Increase of hydrogen bonds between fibers Increase of filler retention due to ionic character Protective colloid for ASA emulsification Increase of dry substance in the press section of the paper machine
63. Starch Convention Martin Kozich

Retention aid
Sizing

Drainage
18th of April 2012

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

18th of April 2012

63. Starch Convention

Martin Kozich

Chemically modified starches for adhesives

Starches for paperbag gluing

Advantages of chem. mod. starches
High tack

Minimal splashing Excellent viscosity stability Excellent runability

Wheel gluing unit

Bottom gluing
18th of April 2012 63. Starch Convention Martin Kozich

Chemically modified starches for adhesives

PRINCIPLES ABOUT WORKABILITY OF STARCHES
for paperbag gluing why crosslinking?

18th of April 2012

63. Starch Convention

Martin Kozich

Chemically modified starches for adhesives

PRINCIPLES ABOUT WORKABILITY OF STARCHES
for paperbag gluing why crosslinking?

no splashing

high splashing

18th of April 2012

63. Starch Convention

Martin Kozich

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

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

Sizing of fiber

18th of April 2012

63. Starch Convention

Martin Kozich

Chemically modified starches for sizing

Investigation of starch films test for tensile strength / elongation

native potato starch

ox potato starch

hp-ox potato starch

native corn starch

18th of April 2012 63. Starch Convention Martin Kozich

Chemically modified starches for sizing

Determination of desizability remaining starch by iodine test
Scale of purple

Completely desized (modified)

Partly desized (not modified) Sized textile

18th of April 2012

63. Starch Convention

Martin Kozich

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

18th of April 2012

63. Starch Convention

Martin Kozich

Chemically modified starches for dry mortar

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. J.I.lvarez et al. Carbohyr. Polym. 80, 222 (2010)
A. Glatthor, Schleibinger Rheologie-Kolloquium Regensburg, 2005

Aqueous viscosity
18th of April 2012 63. Starch Convention

Slump flow
Martin Kozich

Chemically modified starches for dry mortar

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
Open time Slip resistance

Typ A: highly modified starch Typ A

18th of April 2012

Typ B: unmodified starch

Typ B
63. Starch Convention Martin Kozich

Applications of chemically modified starch

Thank you for your attention Marnik Wastyn Martin Kozich

18th of April 2012

63. Starch Convention

Martin Kozich