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Effect of Retention Aids on AKD Size Response and Permanence

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Effect of Retention Aids on AKD Size Response and Permanence Western Michigan University ScholarWorks at WMU Paper Engineering Senior Theses Chemical and Paper Engineering 4-1995 Effect of Retention Aids on AKD Size Response and Permanence Jeremy Matthews Western Michigan University Follow this and additional works at: https://scholarworks.wmich.edu/engineer-senior-theses Part of the Wood Science and Pulp, Paper Technology Commons Recommended Citation Matthews, Jeremy, "Effect of Retention Aids on AKD Size Response and Permanence" (1995). Paper Engineering Senior Theses. 306. https://scholarworks.wmich.edu/engineer-senior-theses/306 This Dissertation/Thesis is brought to you for free and open access by the Chemical and Paper Engineering at ScholarWorks at WMU. It has been accepted for inclusion in Paper Engineering Senior Theses by an authorized administrator of ScholarWorks at WMU. For more information, please contact wmu- [email protected]. EFFECT OF RETENTION AIDSON AKD SIZE RESPONSE AND PERMANENCE by Jeremy Matthews A Thesis Submitted inPartial Fulfillment of the Requirements forthe Degree of Bachelor of Science Departmentof Paper andPrinting Science andEngineering WesternMichigan University Kalamazoo,Michigan April, 1995 Table of Contents PageNumber Introduction 1 Problem Statement 4 ExperimentalProcedure 5 Results and Discussion 5 Conclusions 11 LiteratureCited 12 Figures,Tables, Charts 14 Abstract Poor size responseand size reversion have been major concernswith the useof an alkyl ketene dimer (AKD)sizing system. Poor retentionof calciumcarbonate fillersand fiberfines are believed to be the cause of poorsize response. A number of materials, includingcarbonate fillers, promotersand retentionaids are believedto contributeto size reversion. The focusof this study was to determinethe effectivenessof retentionaids in obtaining good size response. Size permanencewas also studied The performanceof the retention aides were studied by preparing handsheetsat fivedifferent zeta potentials. It wasdetermined that when no retentionaid wasadded to the system, size responsewas not dependenton zetapotential. It was dependenton theamount of polyethyleneimine(PEI) present in the system. Low sizing levels in the absence of PEI indicate poor retention of the size molecules. When cationicpolymers were added to the stock, sizing levels showed a dramatic increase. This increase was do to superiorretention of the fiberfines. As zeta potential wasincreased to highly cationic,size levels droppeddue to poorretention of the sizing chemical. Cationic polymerwas not observedto contributeto size reversion. Size responsewith the addition of an anionic polymerwas highly dependenton the presence of a cationic fixative. When no PEI waspresent in the stock, the anionic polymerwas ineffective. Small amountsof PEI provided cationicsites forthe anionic polymerto bridge the fibers. Contraryto previous literature studies, the anionicpolymer did not contributeto size reversion. When PEI wasadded to the system, largeincreases in sizing levels were observed PEI promotes excellent retentionof the fiberfines. Good finesretention will increasesizing levels. Not only did PEI promote the reactionbetween AKD and cellulose, no size reversion wasobserved when it wasused Introduction/LiteratureAnalysis Alkalinepapermaking has seen a surge in popularityover thepast decade. In 1991, 26% of printing andwriting paperswere produced by alkaline processes (1). By 1995, that percentagehad increasedto · 65% andis expectedto increaseto 9()0/oby the end of the century(2). Alkaline produced paperhas advantages over acid systemsthat include: improved sheet strength,substitution of calciumcaroonatc for titanium dioxide and improved paperstability on aging. Calcium caroonatefillers arc much more inexpensive than titanium dioxide. Therefore, aslong asstrength and runability requirements can bemet, more fillercan besubstituted at the samecost Calcium carbonatefillers increase opacity, brightness, and print quality(3). Sizing is definedas the abilityof paperto reducethe rateof fluidpenetration. All sizingagents must achieve fourrequirements to develop sizing. First, they mustreduce fiber wetability, which is accomplished by introducinghydrophobic groups at the surface of thesheet. The size must alsobe retained on the fiber, distributedevenly over the fiber surface andbe anchored to the cellulose toprovide goodwater repellency (4). Acid paperis sizedusing the traditional rosin andalum system. Thissystem is not efficientat neutralto alkaline pH,so analternative sizing system must be used. The most popularalkaline sizing agent is alkylketene dimer (AKO). AKDis a synthetic. long-chainorganic molecule that reactsdirectly with cellulose hydroxylgroups to form esters(5). A portionof the AKDremains unbound,but it also contnbutesto sizing (6). AKD alsoreacts withwater to forma 13-ketoacid whichdecomposes to aketone. This side reactionis undesirablesince the ketone doesnot contnbuteto sizing(7). The reactionsof AKD shownare in Figure_t 2 Two major differencesbetween AKD and rosin and alumsizing systems have beenobserved. The firstdifference is in the shapeof the size responsecurves (see Figure 2). In anacid system, rosin is precipitated on the fiberswith alum. Sizing is developed in the dryersection when the rosin is melted andanchored to the fibers. This system is robustand has a fairly constant sizeresponse, even at low additionlevels. Inalkaline sizing systems, a covalent bond is formedto providea stronglink betweensize and fiber. AKDis emulsifiedwith dispersantsand stabilizers to allow preliminarydistnbution to fibersin the stock. This impartsa net cationiccharge to the size which permitsa weak electrostaticbonding with cellulose fibersat the wet end. During drying,size is redistributed over thefiber surface andforms covalent ester bonds with the hydroxyl groupson cellulose molecules. Initial retention is criticalsince the initialelectrostatic link is weak andthe fullcovalent bond does not formuntil the drying cycle. Poor initialretention will result in hydrolysis of the AKD molecule (8). At low AKDaddition levels, emulsion particleshave a moredifficult time in spreadingto cover the entirefiber surface. Thisaccounts for differencesin theresponse curves of acid and alkaline sizing systems, and explainswhy alkaline sizingis moredifficult to control. Anotherdifference between the two sizingsystems is permanence. Rosin and alumsizing maintainsits effectiveness over time. However, AKDsizing hashad many problems with"size reversion,"a loss in sizingover time. The most extremecase of size reversion,where sizing is completely lost, is called fugitivesizing (16). Both typesof sizing loss have beenobserved under many conditions. 3 As mentionedearlier, unbound AKD contributes to the hydrophobicityof the sheet However, this material stillpossesses a potentialfor hydrolysis. If the unreacted size is hydrolyzed, it no longer contributesto sizing. Researchdone by Patton (9) determinedthat up to 85% of theretained A.KOis unbound Marton(7) determinedthat about50% of retained AKD is unbound Both these figuresrepresent the largepotential forthe size to behydrolyzed, causing size reversion. Size reversionhas been observedunder many conditions. Water hardness, alkalinity, promoters, retentionaids and carbonatefillers have all beenaccused of causing sizereversion (10). The focus of researchhas beenon fillersand fiber fines (11). Carbonatefillers and fiber fines have been found to adsorba disproportionate amount of size material due tohigh surfacearea. Filler chemistrydoes not provide an opportunityfor bonding with AKO. Therefore, any AKD which is adsorbedby the carbonateis unbound The key to obtaininggood initial sizing values andpreventing size reversion is to maintain high firstpass retention (12). Good firstpass retention provides two main benefitsto sizing: it preventsAKD hydrolysis in the white water and contributessizing from thefines fraction of thestock. In addition,good firstpass retention is criticalto maintainingthe economic advantageof using calcium carbonatefillers (13). Retentionaids areused to increaseretention of finematerials such ascalcium carbonateand fiberfines. Betterretention of theseparticles increases sizinglevels. With highermachine speeds being used today,there is a need to formfloes which areresistant 4 higher machine speedsbeing used today, there is a need to formfloes which are resistant to shear. Most of these retentionaids have a high molecularweight and are polyacrylamide-based. An excellent review of retentionaids wasdone by Hubbe(14). Thereare several other advantages to using retentionaids. By increasing drainage,they increasewet-web strengthwhich canre.duce the numberof wet-web breaks. In addition,better wet-web strength allows papermakersto usea greateramount of recycled fiberin the product (15). Retentionaid perfonnance is highlydependent on the zetapotential of the solids in the system ( 17). Zetapotential is a measureof the potentialof a particleat its shear plane. Zetapotential is controlledon thepapermachine to maximizeretention of fibers, fillers, finesand dyes(17). Cellulose fibersare anionicallycharged due to carboxyl groups on the hemicelluloses anddue to lignosulfonates. Theaddition of cationic materialto the fibrous system will affect zeta potentialby adsorbingon thesurface of the particle. Therefore,by addinglow molecularweight, highly cationicmaterials such as alumor polyethyleneimine(PEI), the zeta potentialof thecellulose fibersincreases from negativeto positive. Problem Statement Under certainconditions, AKO size
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