Chapter 5: Retention In Neutral And Alkaline Papermaking 61 CHAPTER 5 Retention in Neutral and Alkaline Papermaking Francis G. Aloi National Starch and Chemical Co. Bridgewater, NJ, USA Ralph M. Trsksak National Starch and Chemical Co. Bridgewater, NJ, USA Since the advent of alkaline papermak- ing in the early 1970s, several new chemi- caf additive syscems have been developed to provide increased fine particle reten- tion, In traditional acid papermaking, tetention was obtained mainly by utilizing electrolytes, such as alum, and cationic flocculants. Today, newer technology, based on microparticle systems, joins’ traditional dlectrolytes and polyelectrolytes to provide high levels of retention. Microparticle retention systems rely on coagulation via charge neutralization as ary primary mechanism for retention performance. Coagulation allows fora high level of pig. ment retention, without sacrificing sheet formation, Retention in alkaline papermaking is significanely different than acid paper- making, both mechanically and with respect to the chemical mechanisms which are developed. Recent trends such as increased incorporation of recycled Aber and decreased fresh water usage have resulted in systems with much higher dis- solved and suspended materials. These sys- tems are characterized by significandy higher condueeiviey As a fesuf, alkaline high conductivity systems require novel approaches to obtain maximum retention. Why retention differs in alkaline papermaking Retention of fine solids, in both acid and alkaline papermaking, is controlled by several factors. These are usually divided into two categories: mechanical factors and the so-called physio-chemical factors Working together, they control overall paper machine drainage and retention. Mechanical factors include mechanical entrapment of small particles and the rate and manner by which the paper web is formed on the wire (1):This is generally referted to as mechanical filtration. The general consensus in the literacure is that mechanical factors are responsible for most long fiber retention but have only a small impact on fine particle retention (2) The impact mechanical factors play on small particle retention is determined by the size and type of small particles bein, reaained, 25 wel asthe formation rate an structure of the final paper web. The char- acteristics of the paper machine wire also play a role (2). Up to 90% of all small particle reten- tion is controlled by chemical factors. Chemical retention is obtained with the use of functional chemical additives. These include electrolytes, polyelec- trolytes, charged starches, and colloidal microparticles. It generally is agreed that functional additives control and enhance retention by chemical aggregation of small particles. This aggregation is developed by at least one of three mechanisms. ‘These mechanisms are agglomeration, coagula- tion, and flocculation. The definitions of these three mechanisms are as follows (2): Agglomeration: The destabilization of a particle suspension by adsorbing a new charge on the particles’ surface. Flocculation: The destabilization of a article suspension by bonding the parti- Fes together with long-chain charged polyelectrolytes. Coagulation: The destabilization of a particle suspension by changing the ionic62 Retention of Fines and Fillers During Papermaking characteristics of the particle suspension wich salts Some authors refer to coagulation and agglomeration as the same mechanism. As a result, these terms have been used inter: changeably in the literature. Agglomera. tion is a term often used in papermaking, while coagulation is a term most often used in water treatment. * A clear distinction between coagula- tion and agglomeration is made in this chapter. Agglomeration and coagulation both refer to particle destabilization via alteration of the charge on the particles surface. In coagulation, however, the over. all system charge is close to a zero zeta- potential. Agglomeration, on the other hand, refers to a situation where one charged particle is aggregated co other charged particles by a ference in charg, This distinction between agglomersiee and coagulation is significant and. will become more apparent when various alka- line retention systems are discussed later in the chapter, Icis important to note that while each mechanism is unique, there is one com- mon theme. Each mechanism impacts small particle aggregation by system de- stabilization using some type of charged chemical additive. Since most solid parti- cles used in papermaking are anionic, cationic charge plays an important role, Charge, especially cationic charge, is the vehicle by which these mechanisms oper- ate, To understand this concept is to understand why chemical reention in alkaline papermaking is significandy ferent from retention in acid. papermake ing, Early proponents of alkaline paper- making believed the only major cfference between acid and alkaline papermaking was the system pH and the ability to use calcium carbonate in place of filler clay. While this is far from accurate, pH alone is a large enough difference to alter chem- ical drainage and retention completely. The pH is a log scale measurement, so a one unit change in the pH is a cenfold change in the concentration of the H> ions. When an aqueous system, such as 2 papermaking system, goes from a pH of 5.0 to a pH of 8.0, the concentration of the H’ ions in the system is 1000 times lower. The system is now rich in HO. ions. Since all retention mechanisras tely on charge and most functional additives are ionically charged, their functionality is significantly impacted by a change in pH of 5.0 to 8.0. Most cationically charged additives used in papetmaking incorporate some type of functional amine. An amine is a molecule that contains a nitrogen atom, Primary, secondary, and tertiary amines, have one, vwo, or three alkyl groups, respectively, bound to a nitrogen atom, In water, H* ions associate with the amine to given an ammonium salt. The protonated amine has a cationic charge. Alkaline con- ditions deprotonate the cationic ammoni- uum salt to give the neutral amine salt. The cationic charge of the additive is signifi- cantly reduced (4). Figure 1 illustrates this process ‘The move to alkaline papermaking has created a need to develop new cationic starches and polymers based on quater- nary amines. These maintain their cation- ic charge over the entire papermaking pH range as compared to tertiary amines, which become less cationic under alkaline conditions. As with the cationic functional amines, anionic functional carboxylic acid groups are affected by pH. At an acidic pH, H* ions protonate and neutralize the anconic charge on carboxylic acid groups. Under alkaline conditions, the carboxylic acid is deprotonated, producing an anionic func- tional group. Anionic acrylic acid/poly- acrylamide copolymers were used ony t0 a limited extent in acid papermaking. ‘Today, they have become important high molecular weight flocculants in alkaline papermaking.cale measurement, sp ‘the pH is a tenfold ntration of the Hr ous system, such as a oes from a pH of J the concentration of ystem is 1000 times is now rich in HO ion mechanisms rely functional additives their functionality is iby a change in pH 7 charged additives 8, incorporate some nine. An amine is a ns a nitrogen atom, and tertiary amines, three alkyl groups, a nitrogen atom. In te with the amine to salt. The protonated charge. Alkaline con- ne cationic ammoni- atral amine salt. The e additive is signifi gure I illustrates this ine papermaking has svelop new cationic ss based on quater- aintain their cation- ire papermaking pH co tertiary amines, ionic under alkaline ¢ functional amines, oxylic acid groups Acan acidic pH, Ht sutralize the anionic acid groups. Under 1¢ carboxylic acid is ing an anionic func- c acrylic acid/poly s were used only to acid papermaking me important high eulane in alkaline Chapter 5: Retention In Neutral And Alkaline Papermaking 63 Figure 1. Effect of pH on the charge of various polyelectrolytes 100% | 100% |[<——>}- 100% J¢<——— + ov] Cationic quaternary amines Cationic tertiary amine Anionic copolymer -|<————+ [100% 1100% | 0% l« 0-100% 50-80% Legend: % of functional charge on polyelectrolyte ol | Vos 0 2 4 6 pH Rosin, a complex mixture of carboxylic acids (obtained originally from sofewood twees), has been used for almost a century in acid papermaking as an internal sizing agent. The main components of rosin are mono and tricyclic acids, often referred to as rosin acids. Today, all rosin acid deriva- tives are in a tricyclic acid form, because they are made with fumaric acid. Addi- sional acid groups are introduced into rosin by reaction of the rosin with maleic anhydride. At a pH of 4.2 to 5.5, these carboxylic anhydrides are relatively stable to hydrolysis (rosin’s carboxyl group plays a key role in the development of sizing) (5). Ac an alkaline pH, the HO ions attack the anhydride, saponifying it and thus adding an anionic functionality in the process. As-a result, rosin’s ability to function as a hydrophobic molecule begins to decrease at a pH above 6.5. For this reason, rosin cannot be effectively used in alkaline papermaking. Synthetic internal sizing agents had to be developed before alkaline papermaking could com- pete with traditional acid papermaking By the late 1960s, two synthetic internal sizing agents had been invented, alkyl 8 10 12 ketene dimer (AKD) and alkenyl succinic anhydride (ASA). Although boch func- tional additives have increased the com- lexity of alkaline papermaking and have cen plagued with problems, they remain the dominant internal sizing additives used in papermaking today. ‘The papermaking fibers themselves are changed as a result of changes ia pH. Cellulose is naturally anionic due to the presence of carboxylate groups on the fiber’s surface. Carboxylate grouzs are anionic under acidic conditions, and become more anionic as the pH rises into the alkaline range. At an alkaline pH, the fibers uncoil to a greater extent than they an on the acid side and their susface Ab- rils extend outward to a greater distance (. This results in fibers that have more exposed surface area for fiber-to-fiber bonding. This extended fiber structure is desirable for strength development, but usually impedes drainage. More fiber-to-fiber bonding (higher strength) does allow more internal filler to be used. Alkaline papermaking has allowed the use of calcium carbonate in