Starches for Use in Papermaking

The major starch sources are corn, potato, waxy maize, wheat and tapioca. Refined starches are supplied in powder form or as slightly aggregated pearl starch.16 Unmodified (native) starch is rarely used in the paper industry, except as a binder for laminates and in the corrugating process. Most starches for use in papermaking are specialty products that have been modified by controlled hydrolysis, oxidation or derivatization.17 

Acid-hydrolyzed (thinned) starches are produced through depolymerization by hydrochloric or other acids.18,19 Their low viscosity stability restricts their utilization in paper mills. They are used primarily for surface sizing at the size press or at the calender stack. 

Anionic starches are obtained by reaction with phosphoric acid and alkali metal phosphates or by derivatization with carboxymethyl groups.30,31 This modification is primarily used to introduce amphoteric properties into cationic com starch for application on the wet end of the paper machine. Anionic starches with carboxymethyl substitution are used as thickeners in coating colors or as binders in coatings for specialty paper grades. Oxidized starches are inherently anionic but without thickening action. Potato starch already carries sufficient natural anionic charge to provide amphoteric properties after cationization.32 

Hydrophobic starches are generated by a variety of reactions, for example by esterification with octenyl-substituted succinic acid anhydride.39 They can have the properties of a polymeric surfactant, which will generate a weak network with dispersed 

Aldehyde starches are prepared by treatment with periodic acid/periodate ions, which selectively oxidize the adjacent hydroxyl groups on carbon atoms 2 and 3 to aldehyde groups. Dialdehyde starch can react with cellulose by forming covalent hemiacetal and acetal bonds.40 It is primarily used as a wet strength agent in the production of tissue and other sanitary grades. 

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Starch for use in papermaking has to meet specific purity requirements in residual oil, protein, bran and ash content. Industrial starches have a protein content (N X 6.25), ranging from about 0.05% for potato starch to 0.3-0.6% for com starch, depending on separation efficiency during production. Excess protein content will induce foaming in dispersions of starch and affect the quality and strength of the coated surface. Starch for use in the paper industry should not contain more than 0.4% protein. Oxidized starches tend to have the lowest protein content. Residual oil will cause retrogradation due to complex formation with amylose. 

Starch monophosphates are quite useful in foods because of their superior freeze—thaw stabiUty. As thickeners in frozen gravy and frozen cream pie preparations, they are preferred to other starches. A pregelatinized starch phosphate has been developed (131) which is dispersible in cold water, for use in instant dessert powders and icings and nonfood uses such as core binders for metal molds, in papermaking to improve fold strength and surface characteristics, as a textile size, in aluminum refining, and as a detergent builder. 

Starch is an abundant, inexpensive polysaccharide that is readily available from staple crops such as com or maize and is thus is mostly important as food. Industrially, starch is also widely used in papermaking, the production of adhesives or as additives in plastics. For a number of these applications, it is desirable to chemically modify the starch to increase its hydrophobicity. Starch modification can thus prevent retrodegradation improve gel texture, clarity and sheen improve film formation and stabilize emulsions [108], This may, for example, be achieved by partial acetylation, alkyl siliconation or esterification however, these methods typically require environmentally unfriendly stoichiometric reagents and produce waste. Catalytic modification, such as the palladium-catalyzed telomerization (Scheme 18), of starch may provide a green atom-efficient way for creating chemically modified starches. The physicochemical properties of thus modified starches are discussed by Bouquillon et al. [22]. 

Starches may be used directly as feedstocks, or in more technical uses in modified form (typically as starch esters and ethers), or simply converted to glucose syrups for use in industrial fermentation processes or for onward conversion to isoglucose (fructose). After use of unmodified starches in ethanol production, the largest industrial user of both unmodified and modified starches is the papermaking... 

Early cationic starches were tertiary aminoalkyl starches. Tertiary amines require a proton to remain cationic and were suitable for use in acid papermaking systems. At increasing pH levels, the tertiary amine eventually looses its charge. Quaternary amines remaining cationic throughout the papermaking pH range and now represent the majority of cationic starch types. 

Water molecules are so small and cellulose and so hydrophilic that this solution usually affords only temporary protection. Formaldehyde, glyoxal, polyethylen-imine, and, more recently, derivatized starch (50) and derivatized cationic polyacrylamide resins (51) have been used to provide temporary wet strength. The first two materials must be applied to the formed paper, but the other materials are substantive to the fiber and may be used as wet-end additives. Carboxymethylcellulose-calcium chloride and locust-bean gum-borax are examples of two-component systems applied separately to paper that were used to a limited extent before the advent of the amino resins. Today three major types of wet-strength resins are used in papermaking polyamide-polyamine resins cross-linked with epichlorohydrin (52) are used in neutral to alkaline papers cationic polyacrylamide resins cross-linked with glyoxal are used for acid to neutral papers and melamine-formaldehyde resins are used for acid papers. 

Like the natural gums, starches need to be cooked in water to form dispersions for addition to the papermaking system. Various techniques have been developed for cooking starches rapidly (see Starch). In general, anionic starches are used with alum, which aids in starch retention. The cationic and usually the amphoteric starches are self-retaining. 

Enzymes in Pulp and Paper Production. Enzyme-modified starch has been used for adhesives to strengthen paper base and for surface coating. Developments since the late 1980s of further uses of enzymes in papermaking include pitch control and bleach boosting, (see Paper Pulp). 

Further improvements in the retention of pigment in the paper and enhanced sheet formation are obtained when amphoteric starches are used. Phosphate groups have to be added to cationic cornstarch to produce amphoteric properties. Cationic potato starch has a natural source of anionic charge due to its phosphate content. In recent years, waxy com starches, which consist entirely of amylopectin, have been modified for use as cationic or amphoteric agents for papermaking and surface sizing. 

Most frequently, com or potato starches are used, but there are also applications of wheat starch, rice starch, tapioca starch and others. Recently, waxy maize starch has found commercial application in the manufacture of paper. Thermally dispersed or pregelatinized unmodified starches are used for paper strength improvement by addition to the furnish or by spraying onto the papermaker s wire. 

The use of starch in papermaking is probably one of its oldest non-food applications. An old Egyptian paper document dating from 3500 bc shows that starch was already used for sizing. Starch as a sizing agent was also used in China, as documented by a paper document dating from ad 312 that was sized with starch. 

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