Control of tacky deposits on paper machines – A review

Martin A. Hubbe, Orlando J. Rojas, and Richard A. Venditti, North Carolina State University, Raleigh, NC, USA

KEYWORDS: Deposit control, Detackification, Fouling, 1998; Back, Allen 2000). In this account we consider the
Pitch, Stickies fundamentals of the various treatments available to
combat a diverse range of tacky deposits. A broad
SUMMARY: Wood-derived pitch and tacky materials of approach is used, since chemicals that are effective for
synthetic origin in recovered fiber streams often cause serious
combating one type of tacky material may or may not be
deposit problems on papermaking equipment. Ideally such
materials would be completely removed in processes such as
effective for others.
screening, cleaning, washing, or flotation de-inking. In practice, Although there are some characteristic differences
tacky materials that remain in the fiber furnish can build up among the types of tacky materials found in papermaking
within paper machine headboxes, forming fabrics, press sec- systems, there also are some common features. For
tions, and dryer sections, reducing production efficiency. instance, wood pitch components, waxes, defoaming
Product quality is likely to suffer, especially if deposited materi- chemicals, and pressure-sensitive adhesives all tend to be
al ends up in the sheet. This review considers a variety of che- relatively insoluble in water. Significant deposition
mical additives that papermakers have used to combat deposit problems typically involve temperatures that exceed the
problems. The premise of this article is that knowledge of the glass transition point of at least one component of the
chemistry and colloidal behavior of existing deposit-control organic materials present (McLaren 1948; McLaren,
agents can guide us in the selection, usage practices, and further
Seiler 1949; Comyn 1997; Knubb, Zetter 2002). The
development of strategies for the control of tacky deposits,
especially in the case of pitch, adhesive-based stickies, and
glass transition point can be defined as the temperature at
wax-like deposits. which a glassy material transitions from a rubbery form
to a liquid-like form. Finally, most serious problems with
ADDRESS OF THE AUTHORS: North Carolina State tacky deposits involve colloidal destabilization by
University, Department of Wood and Paper Science, Box 8005, multivalent cations, charge neutralization, or hydro-
Raleigh, NC 27695-8005, USA. dynamic shear. Particles also can be collected together by
Corresponding author: Martin Hubbe ([email protected]) rising foam bubbles. Temperature changes can render the
materials tackier and therefore more likely to form depo-
A variety of tacky materials are present in papermaking sits. Effects of individual factors, as well as
water systems. These substances are brought into the combinations of factors affecting the likelihood of
process through many different sources and means, deposit formation, have been considered by various
including the raw materials. Tacky materials may come authors (Allen, 1980; Dreisbach, Michalopoulos 1989;
from both virgin wood pulp and recycled waste paper Carré et al. 1998; Back 2000).
(Back, Allen 2000; Dechandt et al. 2004). They can come The word “pitch” is often used to designate tacky
from functional and control additives used in the pulp materials derived from wood (Back, Allen 2000; Ekman,
and paper mill, and also chemicals from recycled paper Holmbom 2000; Qin et al. 2004). The tendency of fatty
containing latex (from coated papers) (Laubach 1994), and resin acids to form films and micelles have been
adhesives, waxes and other hot-melt materials (Patel, elucidated by studies of mono- and multi-molecular films
Banerjee 1999), and elastomers from pressure-sensitive (Swanson, Cordingly 1956; Neuman 1975; Neuman
labels (Doshi 1991; Capozzi, Rendé 1994; Douek et al. 1976; Neuman, Swanson 1980). So-called “stickies”
1997). In most cases a given sample of deposit from a (Doshi 1991; Capozzi, Rendé 1994; Venditti et al. 1998,
paper machine system contains a variety of tacky materi- 2000), which are of particular concern to users of
als mixed together. recycled paper, are most often the result of elastomers
The deposition of organic substances is considered a used in pressure-sensitive label adhesives.
major problem in multiple stages of pulp and paper pro- For various reasons tacky deposits have tended to
cessing. Some of the undesired effects involve increases become an increasing problem in paper machine systems.
in downtime, costs to replace paper machine clothing Trends towards a reduction of the amount of fresh water
(forming fabrics, press and drying felts), more frequent employed in the papermaking process have generally
paper breaks (and related cleanup downtime), reduction increased the levels of colloidal substances in paper
of product quality (fish eyes, pinholes and picking), redu- machine systems. Colloidal substances can build up to
ced operational efficiency (e.g., in washing operations), high levels in cases where the retention efficiency of
and losses in productivity of converting and printing ope- those materials on fiber surfaces is relatively low
rations, etc. (Pietschker 1996; Lindholm 1998; Huhtamäki 2003).
Previous reviews have considered the nature of the Increased recycling of paper, as well as evolving trends in
tacky materials that are often found in analytical tests of printing and adhesive use have tended to increase the
deposits collected on the wetted surfaces of paper levels and diversity of tacky materials entering the
machines (Swanson, Cordingly 1956; Parmentier 1980a; system. Ideally, these materials ought to be removed in
Hassler 1988; Dreisbach, Michalopoulos 1989; Glazer various separation processes associated with repulping
1991; Doshi 1991; Doshi 1992; Carré et al. 1998; Ling the secondary fibers (Hodgson 1997).

154 Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006
 Some leading causes of deposit
Though the present review focuses on tacky materials,
deposits of such materials often occur in combination
formation
with other kinds of organic and inorganic scales or Because the causes of deposits on papermaking equip-
deposits. For instance, some deposits may be mainly cau- ment are linked to the nature of the tacky materials, we
sed by slime bacteria or fungi (Nahley 1995; Edwards first discuss briefly the chemical characteristics of the
1996; Anstey et al. 1998; Simons et al. 2004). Such most important components in these substances. Wood
deposits often can be mitigated by use of organic itself contains a large variety of resinous substances. The
biocides, oxidizing agents, surfactants, and enzymes. In chemical nature and concentration of these resinous sub-
addition, tacky deposits may be accompanied by stances depends heavily on the type of fiber (softwood,
precipitation of inorganic scale (Amjad 1995; Potter hardwood, and non-woody plants), the specific specie,
1996; Amjad et al. 2000; Wang 2002). and even the season of harvesting. Table 1 provides a
simplified comparison of the nature and concentration of
Summary of types of additives effective resin compounds in softwoods and hardwoods (Ekman,
against deposits Holmbom 2000).
Chemical antidotes to combat tacky deposits on paper
Table 1. Major wood resin compounds in pine softwood and aspen hardwood
machines are, if anything, even more diverse than the (Ekman, Holmbom 2000).
deposits themselves. Later sections of this article focus
on different classes of deposit-control treatments. These % based on dry wood

include absorbent materials, multivalent cations, poly- Component pine (softwood) Aspen (hardwood)

electrolytes of various degrees of charge density and Fatty acids 0.02 0.09
hydrophilic or lipophilic character, inorganic dispersants, Resin acids 0.32
surfactants, solvents, biocides, and enzymes. It is com- Sterols 0.07 0.06
mon for two or more such approaches to be applied Steryl esters 0.13 0.64
Neutral diterpenoids — 0.01
simultaneously, often at different points in the paper-
Waxes — 0.01
making process. Overall, there is continual development Mono-/di-/triglycerides 2.57 1.55
of anti-deposit treatments, usually with a goal of decrea- Total 3.10 2.36
sing the cost of first-quality paper production. Some
newer developments have been motivated by a desire to
minimize various environmental impacts (Anastas et al. Virgin fibers are typically the main source of natural and
2001; Allen 2002). modified resinous materials present in papermaking
process streams. Vercoe et al. (2005) showed that the
Removal during repulping and de-inking deposition tendency of pitch droplets composed of
To place the present review in context, it is usually recom- triglycerides and resin acids was strongly influenced by
mended to deal with tacky materials in the furnish during their relative solubility in water under ideal laboratory
pulping, rather than during papermaking. By removing conditions. Deposition increased with increasing hydro-
tacky materials earlier in the process, the vulnerable and phobic character. Surprisingly, the effects of unsaturated
somewhat delicate parts of the paper machine system can bonds within the fatty acid groups had a greater influence
be spared. Removal technologies, including screening, clea- than the molecular masses of the tacky materials under
ning, washing, and flotation have been reviewed by others the conditions of study.
(Allen 1980; Moss 1997; Hodgson 1997). Tacky materials Recycled fiber brings additional contaminants, in-
are also often removed during de-inking operations cluding pressure-sensitive adhesives, hot melts, waxes,
(Williams 1987; Borchardt 1992). and latexes. Any dispersants, minerals, defoamers, etc.,
Removal of tacky materials early in the recycling which are added to the system during the papermaking
process also is recommended because subsequent process, augment the chemical variety and complexity of
screening and pumping operations can break down tacky the tacky substances to be dealt with. It would be an
particles into smaller sizes, increasing the difficulty in impossible task to give a full account of all components
removal. As an example, it has been shown that pressure present in the water systems in a papermaking process. A
screening, considered the most effective method to more generic approach for the definition and charac-
remove pressure sensitive adhesive (PSA) particles, can terization of tacky substances relies in their thermo-
under common conditions generate three times the dynamic nature (e.g. surface energies), including the way
number of PSA particles than entering the operation various components interact with other substances (i.e.
(Lucas et al. 2001a,b). As a consequence, the resulting colloidal stabilization or destabilization).
particles have an average size of about one-third that of
the feed. Dispersed phases, thermodynamic instability
Finally, if removal measures are inadequate, on-machi- The underlying cause of most tacky deposits in paper
ne chemical treatments for tacky materials are often mill systems can be described as thermodynamic insta-
accompanied by mechanical methods. One of the most bility of various materials in the water phase (Derjaguin,
popular of these is the placement of doctor blades on Landau 1941; Verwey, Overbeek 1948; Heimenz,
dryer cylinders to continuously remove tacky materials Rajagopalan 1997). At the limit of long equilibration
(Brink 1997). times, thermodynamic processes favor the adhesion and

Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006 155
mixing of materials that have similar solubility chara- perature, Tg (McLaren 1948; Comyn 1997). Tackiness is
cteristics. Solubility of a material often can be predicted difficult to predict, however, since the value of Tg can be
based on components of interactive energy, including reduced by water (Back and Salmén 1982; Salmén et al.
dispersion force (van der Waals) and acid–base 1985; Olsson, Salmén 2004), or other materials such as
components, as well as hydrogen bonding characteristics the surfactants used in dissolved air flotation (Elsby
(Comyn 1997; Barton 1982). Similar considerations 1986). Simply noting the Tg of the pure component
govern whether liquid droplets of tacky materials will or materials is not an adequate predictor of tack in a
will not spread onto solid surfaces with which they may complex system. Reduced tackiness may be observed if
collide (Voue et al. 1998). The law of thermodynamics the temperature becomes high enough to substantially
favors coalescence of tacky materials and their separation reduce the viscosity of the material (McLaren, Seiler
from the aqueous phase. Fortunately, within the processes 1949). This general type of temperature-dependency has
of pulping and papermaking there are many potential been found to govern the deposition tendency of alkylke-
opportunities to influence the rates and manner of this tene dimer (AKD) sizing agent (Knubb, Zetter 2002), as
phase separation. For instance, by various chemical treat- well as latex products used in coating that can return to
ments, deposit formation may be greatly slowed down, or the paper machine as “white pitch” from coated broke
the offending material may be encouraged to precipitate (Vähäsalo, Holmbom 2005).
onto fibers or absorbent materials, rather than onto
papermaking equipment (Dreisbach, Michalopoulos Brownian motion and flow as mechanisms of
1989). destabilization
To understand what causes tacky materials to come out Starting with the work of Smoluchowski (1903, 1917;
of suspension and form deposits at significant rates, one Hiemenz, Rajagopalan 1997) it has been understood that
needs to consider ways in which tacky particles may be tiny particles in suspension experience random, jerky
stabilized in a suspension. The two most important motions related to their thermal kinetic energy. The
mechanisms to inhibit deposition or agglomeration are immediate cause of each change in direction can be
electrostatic repulsion and steric stabilization. Our under- attributed to a collision between the particle and an
standing of electrostatic forces in stabilization against adjacent molecule in the solution. Brownian motion, as
coagulation has progressed rapidly, with major theo- described, is a primary cause of diffusion of molecules
retical advances starting in the 1940’s (Derjaguin, Landau and small particles, especially in the absence of flow.
1941; Verwey, Overbeek 1948). It has been shown that Brownian motion can explain, for instance, why it is
the buildup of counter-ions, present in the so-called possible for tacky particles to collide with each other and
diffuse layer adjacent to like-charged surfaces, tends to grow into larger agglomerations even in stagnant tanks.
slow down their rates of collision, even in the presence of Rates of Brownian collision among spherical particles
Brownian motion or convective flow (Hogg et al. 1966). or between spheres and flat substrates can be accurately
As we will see, charge stabilization, acting alone, tends predicted in certain situations. For instance, calculations
to be vulnerable to various destabilizing factors present can be carried out if known electrostatic forces of
in industrial processes. repulsion are acting between the surfaces. Rates of
By contrast, steric stabilization involves the adsorption coagulation have been found to depend on the height of a
of relatively long-chain hydrophilic groups, which may barrier of free energy that opposes collision between the
be either in the form of polymers or surface-active suspended particles or droplets when the surfaces have
agents. Close approach of surfaces coated by such the same sign of electrical charge (Derjaguin, Landau
hydrophilic layers involves an energetically unfavorably 1941; Verwey, Overbeek 1948; Hogg et al. 1966;
compression of the molecular chains extending outwards Hiemenz, Rajagopalan 1997). Calculation is especially
from each surface (Napper 1977; Rojas et al. 1998; simple in cases where there is no net inter-particle
Morra 2000; Nnebe et al. 2004; Stubenrauch et al. repulsive force, leading to the so-called “rapid coagula-
2004a,b). Steric stabilization has been demonstrated in tion” considered by Smoluchowski (1903, 1917). As will
the case of wood pitch in the presence of hemicellulose be discussed later, various chemical additives can either
components (Clas et al. 1993). The dependency of pitch neutralize or screen the effects of the electrostatic
particle stability on steric stabilization also has been repulsive forces, leading to coagulation rates that can be
demonstrated by breaking down polysaccharide layers calculated based on the number of particles, their sizes,
with an enzyme (Sundberg et al. 1994a). Enzymatic and their shapes. The following equation predicts the
treatment rendered the pitch particles susceptible to initial rate of doublet formation in a suspension of equal
coagulation at a much lower dosage of cationic polymer. spheres in the absence of flow, under the assumption that
Pressure-sensitive adhesives (Huo et al. 1999, 2001, the spheres attract each other once they approach within
2002) and some toner particles (Snyder, Berg 1994; Zeng several nm of each other (Hiemenz, Rajagopalan 1997),
et al. 1999, 2001) have been shown to be sterically
stabilized by starch. Rate = - [8 kT / (3η)] No2 [1]
The word “tack” can be defined as the tendency of a
material to remain stuck following such a collision. A In Eq [1] k is the Boltzmann constant, T is absolute tempe-
substance suspended in water can exhibit tackiness only rature, η is the dynamic viscosity, and No is the initial num-
if the molecules facing the water are mobile; in other ber concentration of the particles in suspension.
words the material must be above its glass transition tem- Flow conditions can greatly accelerate the deposition

156 Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006
of tacky materials, especially when the particles are 1956). It follows from this equation that rates of gravi-
relatively large. Estimates of the hydrodynamic shear tational separation are directly proportional to the diffe-
stress at different locations within a typical paper rence in densities of the two phases. The rates of settling
machine system generally lie within the range 10 to or creaming of spherical particles also are predicted to be
20,000 Pa (Tam Doo et al. 1984). Eq [2] describes rates proportional to the radius. In the case of liquid droplets
of inter-particle sticking collisions in turbulent flow the rates of gravitational separation can be greatly
(Saffman, Turner 1956; Swerin, Ödberg 1997; Huang, increased by coalescence, increasing the value of the
Pan 2002): effective radius. The situation is admittedly more
complex in the case of solid particles, though it is often
Rate = 4/3 α ( ε /ν )0.5 (α1 + a2)3 No2 [2] satisfactory to define effective values of the radius and
density terms in Eq [3]. Similar considerations govern
where α is a coefficient giving the probability that a the rising of bubbles, as in the case of flotation de-inking
given collision results in sticking, ε is the rate of energy (Heindel 1999).
dissipation in turbulent flow, ν is the kinematic viscosity,
and a1 is the radius of one of the colliding particles, Chemically induced destabilization
treated as a sphere. Suspensions of resinous materials that are stabilized by
Although Eq [2] can provide reasonable estimates of charge repulsion alone often can be coagulated by
inter-particle collisions in practical applications, hydro- increases in electrolyte content or water hardness (Farley
dynamic effects can greatly influence the probability of 1977; Allen 1980; Hassler 1988; Abraham 1998; Pelton,
collisions of materials in flowing suspensions. As noted Lawrence 1991; Clas et al. 1993; Huo et al. 2001) or by
by van de Ven and Mason (1981), suspended materials decreases in pH (Sihvonen et al. 1998). Complexation
exposed to simple shear flow tend to avoid each other, between the hardness ions and particles of pitch or
resulting in collision rates far lower than those predicted stickies appears to lessen the negative potential at the
based on the undisturbed streamlines of flow. In parti- particle surfaces. Hardness ions also can make materials
cular, hydrodynamic models predict that very small parti- substantially tackier, as in the case of hydrolyzed alkenyl-
cles, e.g. pitch in a flowing suspension, are relatively succinic anhydride (ASA) sizing agent (Scalfarotto
unlikely to impinge upon the main surface of a fiber. 1985). Decreased pH, within the range 7 to about 3, tends
Rather, a much higher relative rate of collision would be to protonate carboxyl groups, which are often the main
expected when streamlines of flow bring a tiny particle contribution to negative charge of pitch and other tacky
towards a similarly-sized fibril structure at a fiber materials in the wet end of a paper machine. Hardness
surface. Early evidence of preferential deposition of fine ions also can bring about destabilization of wood pitch,
particles onto fibrils (Haslam, Steele 1936) has recently especially in cases where the lipophilic droplets have a
been confirmed by high-resolution imaging of macro- negative charge due to the presence of fatty acid salts
molecular events occurring during the formation of paper (Otero et al. 2000; Qin et al. 2004).
(McNeal et al. 2005). More complete neutralization, and even reversal of
One of the most vexing problems with sticky materials negative charges of tacky materials can be achieved by
in papermaking furnish is that the same hydrodynamic addition of multivalent cationic materials such as alumi-
shear forces that can accelerate deposit problems some- num ionic species (Matijeviç, Stryker 1966; Ormerod,
times have the opposite effect of tearing the tacky Hipolit 1987; Hassler 1988; Bottéro, Fiessinger 1989) or
material into finely divided fragments or droplets that are strongly cationic polyelectrolytes (Winter et al. 1992;
very difficult to retain during the formation of paper. Shetty et al. 1994; Richardson 1995; Colman et al. 1996;
So-called microstickies (Gruber et al. 1998; Menke 1998; Carré et al. 1998; Baumann et al. 2002). Though it might
Huo et al. 2001) appear to form during intense or seem elementary to bring about particle coagulation by
prolonged agitation of stock. Stickies also have a such treatments, the results can be difficult to predict. As
tendency to extrude themselves through screening will be shown later, treatments with highly cationic
devices, especially under industrial conditions involving materials can have various different effects on the tacki-
elevated temperatures and intense pressures (Lucas et al. ness of the resinous material in question (Ormerod,
2001; Flanagan 2002; Venditti et al. 2004). Hipolit 1987; Hassler 1988; Dreisbach, Michalopoulos
1989; Carré et al. 1998). Also, if the level of treatment is
Gravity-induced destabilization sufficient to reverse the charge of the system, then the
Gravity can act in various ways to destabilize suspensions suspended particles can be stabilized by double-layer
of pitchy or sticky particles. Velocities of sedimentation repulsion originated from strong net positive charges of
or creaming of individual, spherical particles are given by the treated surfaces.
the Stokes-Einstein equation,
Scale and inorganic deposits
V = Sqrt [ 8 g ( ρs - ρ f ) α / (3 Cd ρ f) ] [3] Deposits of tacky materials sometimes can occur in
association with scale deposits. By definition, scale
where g is the gravitational (or other) acceleration, ρs is results from the chemical precipitation of inorganic
the density of the solid, ρf is the density of the fluid, a is compounds in locations where the solubility product
the particle radius, and Cd is the displacement factor, between the constituent ions are exceeded. Common
which is equal to 1 in the case of a sphere (Einstein examples of scale-forming compounds, observed in

Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006 157
 Deposit-control agents for tacky
papermaking applications, include silicates (Saasta-
moinen et al. 1995; Froass et al. 1997), barium sulfate substances
(Rudie 2000), and aluminum hydroxide (Potter 1996). Within the paper machine system a variety of strategies
The hardness ions Ca2+ and Mg2+ can interact with anionic have been used to reduce or eliminate problems resulting
species such as carbonate and oxalates, forming insoluble from deposition of tacky materials (Braitberg 1966;
precipitates that tend to be particularly troubling in Parmentier 1980a; Hassler 1988; Dreisbach, Michalo-
papermaking applications. The deposit-control strategies poulos 1989; Glazer 1991; Doshi 1991; Doshi 1992;
to be discussed later in this article are seldom effective in Fogarty 1993; Robertson, Taylor 1994; Blankenburg,
combating scale problems. Rather, most scale problems Schulte 1996; Colman et al. 1996; Gill 1996; Back, Allen
require either efforts to reduce the aqueous concentration 2000; Dechandt et al. 2004). The mechanisms by which
of at least one of the common ions of the depositing inor- such strategies function are not completely understood.
ganic material, or addition of an ionic substance capable However, it still makes sense to categorize the various
of changing the adhesiveness or cohesiveness of the approaches for deposit control as alternatively involving
deposited material. Scale inhibitors are commonly used, adsorbents, multivalent inorganic cations, poly-
including polyphosphates, hydroxyl ethyl diphosphate electrolytes, nonionic dissolved polymers such as polyvi-
(HEDP), poly(acrylic acids), and others. nyl alcohol and mannans, dispersants, surfactants, sol-
vents, enzymes, and also mechanical treatments.
Source-oriented solutions to tacky deposits
Source-oriented approaches can minimize tacky deposits Adsorbent materials
at vulnerable parts of the papermaking process. In parti- Talc has been the benchmark against which many other
cular, deposits that build up within the headbox, on existing or prospective deposit-control treatments are
forming fabrics, in the press section, and on dryer cans often ranked. Talc is a natural magnesium silicate having
have the potential to hurt both the efficiency of the a platy structure, non-abrasive nature (if pure), and a high
processes and product quality in papermaking. affinity towards oleophilic materials (Doshi 1992). Talc
Deposit problems related to wood pitch often can be has two surfaces, an oil-loving (lipophilic) face, formed
minimized by allowing incoming wood chips to stand in by cleavage of the layers and consisting of neutral oxygen
piles for several days or weeks before use (Blazey et al. atoms, and hydrophilic edges. As in the case of “talcum
2002). Benefits of chip aging usually are explained in powder,” which is used for infant care, etc., talc’s oil-
terms of hydrolysis of the triglycerides component for the loving character can cause it to form clumps on the
extractives. Oxidation, which can occur during extended surface of water, rather than becoming dispersed.
aging, increases the hydrophilic character of the wood Nevertheless, application of sufficient agitation, espe-
resins and provides a means by which they can interact cially in the presence of a dispersant (see later), can result
more strongly with soluble aluminum products, which are in a fine particulate dispersion. Talc products used for
often used in pitch-control strategies (see later). deposit control are generally of the “fine” variety, having
Oligomerization among unsaturated hydrocarbon groups particle sizes (equivalent spherical diameters) in the
within resin acid species has a tendency to increase the range of 0.5 to about 20 µm, based on sedimentation
glass transition temperature, sometimes reducing velocity tests.
tackiness in subsequent operations, depending on the Dispersed talc can be applied at various points in the
temperature (Back, Allen 2000). papermaking process, starting with the pulp mill or de-
In the case of recovered fibers, conditions of screening inking plant, and continuing up to the thin-stock recircu-
and other unit operations associated with pulping, lation section of the paper machine. Relatively early
cleaning, or de-inking can be optimized for efficient addition of talc to the process is favored, especially in
removal of sticky materials (Moss 1997; Hodgson 1997). cases where a high proportion of the tacky materials
Recent work showed that conditions of pressure drop and enter from one or more identifiable thick-stock streams
operating temperature during commercial-scale screening or other sources. For example, talc is sometimes added to
operations can tend to be too harsh for efficient exclusion de-inked pulp or coated broke. Early collection of tacky
of pressure-sensitive adhesives (Lucas et al. 2001; particles onto solid surfaces in suspension helps to mini-
Venditti et al. 2004). It follows that modified operating mize the likelihood that they agglomerate together,
conditions and/or equipment design have the potential to forming deposits large enough to hurt the appearance of
reduce the amounts of sticky materials that reach later the resulting paper. In general, the target material(s) need
papermaking operations. By contrast, application of to already be tacky under the process conditions of
excessive levels of hydrodynamic shear during repulping papermaking, not just under the elevated temperatures of
can separate adhesive material into very small particles, drying, in order for talc addition to be effective (Doshi
known as micro-stickies (Gruber et al. 1998; Menke 1992). It is recommended to use an effective retention aid
1998; Huo et al. 2001). Though many problems related to system so that talc laden with tacky substances becomes
removal of stickies appear to be solvable by known purged from the recirculating process water of the paper
separation methods, future papermakers can expect to machine. Very small tacky particles incorporated into the
face an increasingly bewildering array of new or paper product, in conjunction with talc, seldom cause
modified sticky materials in recovered fiber supplies concerns to the end-user. Finally, the main advantage of
where the combination of mechanical and chemical using talc is its low cost and ease of use compared to
approaches are potentially more effective. some of the alternatives.

158 Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006
In the case of wood resins, various evidence favors an
“adsorbent” model to describe talc’s function (Gill 1974;
Mosbye et al. 2003). This model is illustrated schematically
in Fig 1 for the case of very small tacky materials. In sup-
port of this model, addition of talc has been found to sub-
stantially reduce the number concentration of pitch parti-
cles visible in paper machine process water, based on
microscopic counts (Parmentier 1980b). Allen (1980)
observed as many as 14 pitch particles adsorbing onto a
single particle of talc. A substantial decrease in overall
tackiness is expected whenever organophilic materials
become sandwiched between two plates of talc (Gill 1974). Fig 1. Model of talc as an absorbent and detackifier.
Addition of low amounts of talc often can result in an incre-
ase in the net mass of deposited material (Hassler 1988),
giving further evidence to the high affinity between the
materials. By contrast, addition of 0.2% talc, on a volume
basis, was found to reduce the overall tackiness of wood
pitch. For de-inking applications it has been suggested to
add 0.6 to 1.9% of talc, based on oven-dry fiber mass
(Williams 1987).
In addition to the adsorption model, just mentioned, it
also has been proposed that talc in paper machine
systems can change the rheological characteristics of
Fig 2. Model of talc adsorbing to the surface of a large tacky particle.
tacky materials, rendering them non-tacky (Allen et al.
1993). Chewing gum is a familiar demonstration of this
phenomenon; if no talc had been used in its formulation,
gum would stick excessively to the teeth. Talc also appe-
ars to be able to delaminate upon application of sufficient
shear. Presumably such delamination, if it occurs within
an agglomerated mass of talc and tacky materials, would
tend to reduce the dimensions of objectionable materials
(Allen et al. 1993). In other cases, talc has been described
as having poor resistance to hydrodynamic shear (Fogarty
1993), making it essential to verify each application stra-
tegy under commercial conditions.
In addition to the model shown in Fig 1, relatively
small talc particles can attach to larger adhesive particles
such as shown in Fig 2. The coating of talc on the large
sticky particle renders the overall surface less tacky,
discouraging deposition on machinery and paper
machine clothing (Gill 1974; Allen 1980; Doshi 1992;
Shetty et al. 1994; Huo et al. 1999; Huo 2002).
Direct evidence of talc particle adhesion to the surface
of tacky particles was obtained during a thesis project
related to recycling of paper that contains adhesives of
the type used in pressure-sensitive labels (Huo 2002).
Fig 3 clearly shows talc particles adsorbed at the surface
of stickies following agitation of the elastomeric material
in the presence of a dilute dispersion of talc.
Unexpected support for the adsorption mechanism of
detackification was obtained during a study of the effects
of recycling of release liners along with pressure sensi-
tive adhesives (Venditti et al. 2000). It was found that the
presence of release liner material during recycling resul-
Fig 3. Micrographs of particles of elastomeric resin (stickies) agitated in the
ted in a smaller average size of the stickies. As shown in absence (top) and in the presence (bottom) of talc particles.
Fig 4, small flakes of release liner tended to cover much
of the exposed surfaces of the stickie material, making it contrast to talc, bentonite is more water-loving. Also, in
less likely that the particles will collide and stick contrast to talc, montmorillonite is capable of exfoliating
together. much more easily into molecularly thin plates (Knudson
Bentonite is a so-called “swelling clay,” the principle 1993; Rodriguez 2005). Montmorillonite’s physical
mineral component of which is montmorillonite. In properties are profoundly affected by the mineral’s ionic

Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006 159
 to remove wood resins from paper machine white waters
(Bouffard and Duff 1999). A practice of treating minerals
with cationic surfactant for such purposes has been
criticized, since surfactants can desorb from a mineral after
addition to a paper machine system (Carter, Hyder 1993).

Inorganic minerals having positively

charged surfaces...
...sometimes have been used for collection of tacky mate-
rials in papermaking systems. In the distant past it was
sometimes recommended to use asbestos for this purpose
(Woolery 1965). Apparently the naturally cationic nature
of this material was helpful in binding the predominantly
negatively charged colloidal materials found in paper
machine systems. The fibrous nature of asbestos would
be expected to favor its efficient retention in the paper
web, removing the objectionable substances from the
process. Colloidal alumina, produced in a precipitation
reaction, was found to have similar capability (Braitberg
1966). Such materials have long since been discontinued
from papermaking applications due to concerns about
respiratory health.
More recently it has been found that precipitated
calcium carbonate (PCC) can be effective for adsorption
of tacky materials (Whiting 1997). Though the positive
surface charge of pure PCC is relatively weak, charge
still can be expected to play a role in its adsorption of
oleophilic colloids from papermaking processes. PCC is
frequently added in relatively huge quantities, often 10-
30% based on the dry weight of the paper product. The
composite structure of the popular scalenohedral (rosette)
Fig 4. SEM picture of adhesive pulped in the presence of release liner (top) and
without release liner (bottom). form of PCC provides internal voids that would be
expected to be effective for holding onto colloidal
environment. Natural deposits usually are rich in alkaline particles so that they can be purged harmlessly from the
earth cations, and in this form the solids show only process.
moderate tendency to swell in water. Ion exchange, by
treatment with NaOH or KOH, together with the Synthetic, organic fibers...
application of hydrodynamic shear, causes montmo- ...also have been found to be effective for removing tacky
rillonite to exfoliate substantially into its component pla- materials from paper machine process water (Wade
telets. 1987). Polypropylene fibers have an oleophilic surface
Compared to talc, montmorillonite has a much stronger and can be efficiently retained during the formation of
interaction with cationic polymers (Boardman, 1996; paper.
Rojas, 2002). Such interactions are well demonstrated by
the use of bentonite products as agents of retention and Multi-valent inorganic cations and detackification
dewatering. In such applications bentonite products are The use of either aluminum sulfate (papermaker’s alum)
used in conjunction with cationic acrylamide retention or poly-aluminum chloride (PAC) as a component in anti-
aids (Hubbe 2005; Rodriguez 2005). A synergistic effect deposit treatment programs is well known, especially for
has been observed for pitch adsorption, when using bento- systems that contain wood resins (Allen 1980; Dreisbach,
nite products in sequence with a highly charged cationic Michalopoulos 1989; Glazer 1991). In principle it is
polyelectrolyte (Derrick 1994; Boardman 1996). often possible to bring about the agglomeration or depo-
Kaolin clay, though it usually is employed as an ordinary sition of suspended tacky materials by neutralization of
filler material in paper, also can take on the role of pitch their surface charges (Verwey, Overbeek 1948; Hogg et
adsorbent under special circumstances. Ordinary hydrous al. 1966). Aluminum compounds are expected to be
kaolin (Van Olphen 1991) would be expected to be too especially effective for such purposes due to their high
water-loving to be highly active in such a role. However, positive valencies (Matijeviç, Stryker 1966; Strazdins
clay’s ability to take up tacky materials can be greatly 1989; Bottéro, Fiessinger 1989). Ideally, agglomeration is
increased by pre-adsorbing positively charged polymers carried out in the presence of either fibers or another
(Lamar et al., 1990; Curtis et al. 1995) or aluminum ionic suitable adsorbent material (see previous sections), so
species (Hyder et al. 1991; Carter, Hyder 1993; Harrison, that the tacky materials become collected on their
et al. 1996). A similar polymeric pre-treatment strategy surfaces. If not, addition of coagulating chemicals may
also has been applied to zeolites to achieve greater ability merely accelerate self-agglomeration and/or deposition of

160 Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006
the tacky materials onto the wetted surfaces of nation with cationic polymers (Greer, James 1993).
papermaking equipment. Zirconium and titanium salts are also known to react with
Although charge neutralization can explain many of fatty acids and resin acids to form a zirconium/titanium
the effects of aluminum sulfate and related coagulants, it soap which has a higher glass transition temperature, Tg
is also important to consider charge-reversal phenomena. (Buzby, Evans 1991). Most of the organic deposits have a
Multivalent ions of aluminum tend to adsorb strongly glass transition temperature, Tg , within the temperature
onto negatively charged surfaces, giving them a positive range of typical papermaking operations (ca. 30° to
net charge if the dosage is high enough (Matijeviç, 60 °C). Therefore, any treatment that increases the Tg
Stryker 1966). Examples of this phenomenon already above this range has the potential to reduce tackiness and
have been cited, involving pretreatment of clays with diminish deposition problems.
aluminum salts to achieve a positive surface charge Before leaving the subject of detackification, it should
(Lamar et al. 1990; Hyder et al. 1991; Carter, Hyder be noted that the word also is sometimes used to describe
1993; Curtis et al. 1995; Harrison et al. 1996). Attraction the effects of nonionic polymers, such as poly(vinyl
of tacky materials to the adsorbent surfaces is increased, alcohol), methylcellulose, modified poly(ethylene oxide).
since the tacky materials present in paper machine These additives, which will be considered in more detail
systems are usually anionic. later, have been found to be effective detackifiers in some
In like manner, adsorption of aluminum-based material cases (Wang 2002).
onto resinous or sticky materials can be expected to make
the surfaces cationic, such that they have a greater Organic polymers
tendency to be retained onto the generally negative Many of the chemical additives found to be effective for
surfaces of cellulosic fibers and fines. Another control of tacky deposits can be described as organic
consequence of aluminum ions’ adsorption onto resinous polymers. Within this category there are huge ranges of
materials is a more water-loving character. It follows that molecular mass, charge, and water-loving vs. sparingly
a tacky material coated with a hydrophilic layer of soluble character. The effects of polymeric agents are
aluminum hydroxide and related compounds would be greatly dependent on how these materials interact with
less likely to adhere and coalesce with another similar surfaces. Fortunately, these mechanisms are described in
surface in the suspension. a number of reviews (van de Steeg et al. 1992; Fleer et al.
Though aluminum sulfate (alum) can be an especially 1993; Wågberg 2000). The type of polymer employed
cost-effective coagulant under ideal, acidic pH condi- clearly has an impact on the colloidal stability of disper-
tions, there are many situations where greater coagulating sed tacky particles (Dreisbach et al. 1996). Important
efficiency can be achieved with partially hydroxylated classes of polymeric materials used for pitch and stickies
formulations based on aluminum chloride (Strazdins control are considered below.
1989). Such products go by the names of poly-aluminum
chloride (PAC), and aluminum hydroxychloride, etc., and Very-high-mass, acrylamide-based polyelectrolytes...
they contain oligomeric ionic species. The seven-valent ...which papermakers call “retention aids,” are not usually
cation [AlO4Al12(OH)4(H2O)12] 7+ appears to be especially thought of as deposit-control agents. However, their
prominent in many products of this type (Bottéro et al. action in slowing the formation of deposits should not be
1980; Bottéro, Fiessinger 1989; Crawford and Flood overlooked. For example, even when talc is used as a
1989). Such ions appear to be the main chemical species primary deposit-control additive, it is recommended to
involved with soluble aluminum product’s interactions make sure that the talc is being retained efficiently in the
with anionic polymers (Chen et al. 2004). The use of an paper product (Allen 1980; Carter, Hyder 1993).
aluminum chloride-based product for pretreatment of Likewise, when highly cationic additives are used to
clay was noted earlier (Harrison et al. 1996). PAC pro- coagulate tacky materials on the surfaces of fiber fines
ducts also were found to perform very well as part of and other solids (Dreisbach et al. 1988; Horn and Linhart
“passivation” treatments, which will be discussed later 1991; Winter et al. 1992; Shetty et al. 1994; Richardson
(Colman et al. 1996). 1995; Gill 1996; Carré et al. 1998; Baumann et al. 2002),
Work by Dreisbach and Michalopoulos (1989) sugges- it is important to keep these fines from building up in the
ted that alum can render the surfaces of pitch particles short circulation system. This can be achieved either with
more rigid. This effect can be considered as a form of conventional retention aid polymers or with a microparti-
detackification. Similar effects have been observed in cle retention program (Dixit et al. 1991).
studies of monomolecular layers of insoluble fatty acid As illustrated in Fig 5, the mechanism by which high-
salt films spread at the aqueous interface (Swanson, mass acrylamide polymers function has been described
Cordingly 1956). Alum treatment converts such films as polymer bridging (La Mer, Healy 1963; Gregory 1973;
from liquid-like to solid-like in their two-dimensional Swerin, Ödberg 1997). Efficient bridging requires that
phase behavior. the polyelectrolyte interacts with oppositely charged
Similar to aluminum compounds in terms of having a areas on the surfaces with which it comes into contact
small, high-valence, hydroxylated, positive ions, zirco- (Poptoshev, Claesson 2002). Because papermakers often
nium compounds also are useful as detackifiers. employ highly charged cationic materials somewhere in
Zirconium products have been found to be effective in the process, there are usually sufficient anchoring sites
reducing the tack of various polymer-based adhesives, on the solids so that negatively charged retention aids can
either alone (Goldberg 1987; Whiting 1997) or in combi- be used successfully in retention of tacky particles

Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006 161
 Fig 6. Role of high-charge cationic particles in fixing tacky particles to solid surfa-
ces, with involvement of charged-patch mechanism.

Fig 5. Role of very-high-mass acrylamide-based retention aids in retention of stability and adhered to fiber surfaces.
tacky particles. Not to scale, the polymer is shown schematically much larger than The effectiveness of treatment with high-density cationic
actual size to improve clarity of the figure. polyelectrolytes depends on the nature of the tacky
substance. In one study, pitch dispersions that were rich in
(Winter et al. 1992). Alternatively, high-mass cationic triglyceride fats responded well to treatment with a high-
retention aids can interact effectively with uncovered, charge cationic polymer (Hassler 1988). However, another
negative areas on the resinous materials and fibers. suspension, rich in the calcium salts of fatty acids, did not
show a promising response to the same polymer.
High-charge cationic polymers...
...have been found to be effective for deposit control over Hydrophilic polymers of intermediate mass...
a wide range of circumstances (Greer, James 1993; ...are often used for pitch control, and they are sometimes
Magee, Taylor 1994; Richardson 1994; Klein, Grossman classed as detackifying chemicals (Dreisbach, Micha-
1997; Stitt 1998; Kekkonen, Stenius 1999; Song, Ford lopoulos 1989; Ling 1993; Laubach 1994; Richardson
2004; Dechandt et al. 2004). Some of these already have 1995; Nguyen 1996a,b). It makes logical sense that the
been cited in the earlier discussion of certain adsorbent water-hating character of natural and synthetic oleophilic
mineral products (Boardman 1996; Curtis et al. 1995). materials in a paper machine system can be altered by
The high-charge cationic polymers most often used in adsorption of something more hydrophilic onto it
deposit-control applications are quaternary ammonium (Böhmer et al. 1990). By selecting a molecular mass
compounds (Dreisbach et al. 1988) having molecular below about one million g/mole, such effects can be
masses within about 50,000 to 1 million grams per mole. achieved without inducing the kind of polymer bridging
Examples include poly-dimethylamine-epichlorohydrin that was described in the previous section. Polyvinyl
(Greer, James 1993), poly-diallyldimethylammonium alcohol is an example of a product that appears to have
chloride (poly-DADMAC) (Greer, James 1993; the appropriate balance of solubility characteristics to
Richardson 1995; Colman et al. 1996; Carré et al. 1998), work well as a deposit-control agent (Dreisbach, Gomes
and poly-ethylenimine (PEI) (Winter et al. 1992; Colman 1989; Moreland 1989; Nguyen 1996a,b). Other polymers,
et al. 1996; Gill 1996; Baumann et al. 2002). Carré et al. including methylcellulose, modified poly(ethylene
(1998) observed an absence of tackiness following treat- oxide), proteins (Haettich 2002), and hemicellulose com-
ment of a suspension of sticky materials with poly-DAD- ponents (Clas et al. 1993; Otero et al. 2000; Hannuksela,
MAC, whereas treatment with PEI increased the tacki- Holmbom 2004) have shown similar effectiveness. In all
ness under the conditions of testing. Recent work has these cases the polymers are able to adsorb efficiently
demonstrated superior performance of a high-charge onto surfaces that are more hydrophobic than themselves,
cationic polymer having a molecular mass almost as high making those surfaces less prone to adhesion and coales-
as that of typical retention aids (Dechandt et al. 2004). cence. The treated particles are stabilized in the colloidal
Although addition of high-charge cationic polyelectro- system, i.e., their coagulation is inhibited.
lytes to paper machine process streams can achieve The ability of hydrophilic polymers to function as anti-
neutral net surface charges, the mechanisms by which deposit agents can be enhanced by cationic charged
these additives work is expected to be more complex groups in some cases. For instance, certain products
(Shetty et al. 1994). For instance, there is a high classed as organic detackifying agents possess a low
likelihood that such additives cover the surfaces cationic charge density in order to adsorb more effective-
unevenly, giving rise to attraction between oppositely- ly on the surfaces of tacky materials suspended in the
charged patches and uncoated areas on opposing surfaces system (Richardson 1995). Cationic starch, as used in the
(Gregory 1973; Rojas et al. 2002). This mechanism is emulsion of alkaline sizing agents, appears to play a
shown schematically in Fig 6. One study demonstrated similar function in stabilizing oleophilic particles in
the ability of highly charged cationic polymers to suspension (Knubb, Zetter 2002). The effectiveness of a
displace surface-active molecules from the surfaces of certain amphoteric, surface-active protein was enhanced
tacky substances in suspension (Shetty et al. 1994). The by adding it in combination with a high-charge cationic
tacky substances subsequently lost their colloidal polymer (Haettich 2002).

162 Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006
In mechanistic terms, effects of hydrophilic polymers,
having low to moderate charge density, are often said to
function by steric stabilization (Hassler 1988; Sundberg
et al. 1994b; Morra 2000). In other words, the presence
of water-loving tails and loops of macromolecules exten-
ding outwards from the surfaces inhibits close approach
and adhesion between those surfaces (Rojas et al. 1998;
Claesson et al. 2003). Work by Otero et al. (2000) and
Mosbye et al. (2003), among others, showed that steric
stabilization can explain the pitch-stabilizing ability of
carbohydrates dissolved in water from thermomechanical
pulping. In this case carbohydrates adsorb onto pitch Fig 7. Illustration of “minimum-deposition” treatment concept for hydrophilic polymer
layer combining steric stabilization with a minimum dispersion force contribution.
particles and inhibit their deposition onto various mine-
rals, including talc and clay. The tendency of dissolved
starch to stabilize pitch and stickies was mentioned
earlier (Huo et al. 1999; Zeng et al. 2001).

A recipe for a minimum deposition tendency...

...has been described recently (Stenkamp, Berg 1997),
and the approach is worth considering when optimizing
polymer-based detackifying systems. Fig 7 represents of
a type of hydrophilic polymer layer that would be expec-
ted to give superior anti-deposit effects. Characteristics of
such an adsorbed layer are as follows:
· Continuous, dense hydrophilic layer adjacent to the
hydrophobic surface
· Significant steric repulsion between the surfaces when
the longest “tails” of water-soluble polymer begin to
Fig 8. Schematic diagram illustrating effect of dispersant on plot of free energy of
interaction vs. separation distance.
become compressed as the surfaces approach each other
· A minimization of van der Waals (dispersion) forces
between the surfaces, due to the sparcity of the macro
water-loving groups facing toward the aqueous phase. It
follows that treatments with partially hydrophobic poly-
molecules having the highest molecular mass mers may have a net dispersing effect, depending on the
details of molecular structure.
Polyelectrolytes with partially hydrophobic character... Block copolymers, involving hydrophilic and hydro-
...might be thought of as a way to achieve favorable solu- phobic groups, are an extreme example of the principle
bility characteristics between the polyelectrolyte and the just described, and they are reported to work effectively
tacky material, ensuring sufficient adsorption onto tacky as stabilizers for tacky materials in paper machine
materials. The adsorption tendency of polyelectrolytes systems (Fogarty 1993; Ling 1994; Pearson 1995). Block
onto tacky materials can be increased by copolymeriza- copolymers with ethylene oxide and propylene oxide
tion or derivatization with hydrophobic substituent groups (EO/PO) are widely used as a type of polymeric,
groups, such as alkyl chains having 14 to 22 carbons. non-ionic surfactant (Allen 1980; Glazer 1991; Borchardt
Various copolymers of cationic, hydrophilic monomers 1992; Ling 1994; Laubach 1994). By varying the chain
and hydrophobic monomers have shown promise as length of each portion, suppliers of such compounds can
detackifying agents for resinous materials (Finck et al. tailor their properties to satisfy a wide range of
1993; Shetty, Ramesh 1996; Juzukonis, Chen 2000). applications, including emulsification, inverse emulsi-
Alternatively the product may have a hydrophobic mole- fication, wetting, de-inking, and deposit control.
cular chain with hydrophilic pendant groups extending
outwards from the surface(s) into the solution phase. Dispersants
Anionic styrene maleic anhydride copolymer also has Dispersants, when they are recommended for control of
been claimed as a detackifying agent for secondary fibers tacky deposits, usually come with a suggestion to use
(Dahanayake, Yang 2001). As a third possibility, a partial- them in moderation (Allen 1980; Glazer 1991; Gronfors
ly hydrophobic styrene maleic anhydride copolymer can et al. 1991; Carter, Hyder 1993). Too much of a disper-
be blended with cationic guar to achieve a preferred sant chemical is expected to hurt retention efficiency.
balance of properties for stabilization of tacky materials Various dispersant products are classified as inorganic or
(Hlvika, Wai 1996). organic (Hanu 1993). Phosphates are the dominant fami-
The mechanism by which partially hydrophobic ly of inorganic dispersants, whereas acrylate polymers
polymers reduce tackiness is most likely related to their are the dominant family of organic ones.
surface-active character. Briefly stated, it is assumed that The mechanism by which conventional dispersant additi-
a disproportionate number of the oleophilic groups on the ves function in papermaking systems is by contributing a
molecules associate themselves with the surface of the high negative ionic charge to surfaces upon which they
tacky materials. This leaves a disproportionate amount of adsorb (Hanu 1993). As shown in Fig 8, the increased

Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006 163
negative charge of the particle surfaces increases the (Moreland 1986). Typical surfactants used for deposition
electrostatic potential energy barrier, inhibiting contact control include non-ionic, oligomeric compounds such as
between the surfaces. To be effective, the amount of dis- linear alcohol ethoxylates and alkyl phenol ethoxylates.
persant needs to be enough to overpower any coagulants Among the anionic type, alkyl sulfosuccinic acids have
which may be present, e.g. aluminum sulfate or high- been reported. Polymeric surfactants such as EO/PO
charge-density cationic polymers. copolymers and lignosulfates can be also mentioned. A
The use of dispersants has sometimes been criticized large number of patents regarding the use of surfactants
on the grounds that it can lead to uncontrolled buildup of can be invoked, and in the following we will just describe
dispersed materials in a paper machine system (Gronfors briefly their general mechanism of action.
et al. 1991). In principle, unretained fine materials either
must be retained in the paper or they are more likely to Nonionic surfactants...
settle out and build up on papermaking equipment. ...have experienced considerable growth in general
Cationic retention aids, in particular, tend to be deactiva- (Schick 1987), so it is not surprising that the same is true
ted by dispersants. In some cases, however, dispersants with respect to papermaking applications (Allen 1980;
have helped papermakers overcome specific deposit pro- Glazer 1991; Borchardt 1992; Ling 1994; Laubach
blems (Allen 1980; Glazer 1991; Gronfors et al. 1991; 1994). The most popular surfactants in this class fall into
Carter, Hyder 1993). two categories, those in which the hydrophobic portion of
the molecule contains an alkyl group, and those in which
Scale control additives... the hydrophobic portion is a polypropylene oxide block.
...are worth noting at this point, not because they are In either case, the hydrophilic portion usually is compri-
intended for control of tacky deposits, but because their sed of polyethylene oxide (EO), having repeating
properties tend to overlap with those of dispersants –CH2–CH2–O– groups. Superior control of tacky deposits
(Amjad 1995; Wang 2002). Anionic species such as car- was claimed also when a nonionic surfactant solution was
bonates and oxalates have great affinities for metal ions used as the emulsification medium for an organic solvent
such as Ca2+, and Mg2+ and will react to form insoluble (Dreisbach, Champine 2002).
precipitates. The buildup of these precipitates can lead to Fig 9 offers a schematic view of how nonionic
scale deposition in operations such as pulping, bleaching, surfactants are likely to adsorb onto oleophilic particles
and paper production. The most important variables that in such a way that the hydrophilic groups provide a
control the formation of scale include pH, temperature, barrier to contact. A molecular characterization of typical
total concentrations of scale-forming species, and the EO surfactants and their adsorption behaviors on hydro-
presence of other chemicals. Though a discussion of the phobic surfaces can be found in recent publications
physical chemistry of scale formation is beyond the (Stubenrach et al. 2004a,b; Claesson et al. 2005).
scope of this review, suffice it to say that it is a complex Compared to their ionic counterparts, nonionic
subject that involves surface chemistry and heterogene- surfactants are noted for not being affected by pH and
ous nucleation and stability of the various species formed ionic strength (salt). In an aqueous medium they tend to
(Smith, Martell 1989; Wang 2002). It so happens that the adsorb with the non-polar group facing a hydrophobic
multivalent, anionic character of the dispersants descri- surface and with the polar (EO) moieties exposed
bed in the previous subsection tends to make them effec- outwards. The efficiency with which such treatment
tive as sequestrants for multivalent metal ions, such as renders the surfaces hydrophilic and sterically stabilized
calcium. Anti-scale treatments also have been claimed for against sticking collisions can be optimized by varying
use in combination with biocides for deposit control the masses and ratio of masses of the hydrophobic and
(McNeel et al. 2001). hydrophilic parts. In some cases nonionic surfactants may
adversely affect downstream operations. For instance, the
Surfactants amounts of hydrophobic sizing treatments needed to meet
Surfactants can be defined as molecules that have both customer requirements may increase substantially. Short
water-loving and oil-loving groups (Lynn and Bory of froth flotation, little can be done to eliminate the effects
1993). The subject of surfactants already has been of nonionic surfactants, once their intended mission is
mentioned in the context of polymeric materials having
partial hydrophobic character (see Schick 1987; Miller
1988; Doshi 1992), but it is important to recognize that a
wide range of surface-active substances have been found
to be effective in various efforts to reduce deposits of
tacky materials (Hoekstra, May 1987; Scott 1989;
Dykstra, May 1989). As in the case of dispersants,
surface-active additives are expected to adversely affect
first-pass retention (Magee, Taylor 1994). Sizing, dry-
strength, and the rate of dewatering also can suffer,
especially if the dosage of surfactant is enough to
increase the level of entrained air in the system. Foam
generation can be a problem, depending on the detailed Fig 9. Role of nonionic surfactants in forming a stabilizing hydrophilic layer around
nature of the surfactant and the conditions of use a tacky particle.

164 Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006
completed. However, the fact that nonionic surfactants paper machine cleaning procedures. Kerosene products
tend to be highly temperature sensitive, compared to char- used in the paper mill for cleaning or as part of water-in-
ged surfactants, provides a potential way to tune their per- oil emulsions generally have high purity requirements.
formance for different applications. Aromatic compounds are scrupulously excluded from
To address the issue of nonionic surfactants’ expected most applications, since contact of such compounds with
adverse effect on first-pass retention, a series of tests was certain bleaching operations might produce chlorinated
carried out in combination with a cationic acrylamide- compounds of high toxicity. A plant-derived oil,
based retention aid (Capozzi, Rendé 1994, 1995). The limonene, is sometimes used in place of conventional
nonionic surfactant, when first added to the agitated fiber petroleum-based solvents (Chandler 1997).
suspension, caused an immediate increase in the turbidity
of filtrate from the suspension, consistent with a decrease Enzymes
of retention of particulate matter onto fibers. Surprisingly, The majority of “pitch” compounds derived from wood
subsequent addition of the cationic retention aid was highly belong to the family of mono/di/triglycerides, which all
effective, as indicated by very low values of filtrate turbidi- contain ester bonds. Lipases, which hydrolyze such
ty after treatment. Presumably, the molecular mass of the bonds, have been found to be effective against pitch
retention aid was high enough to span the distance between deposits (Skjold-Jørgensen, Lange 1991; Fischer,
the surfaces of fine particles and fibers, even when those Messner 1992; Van Haute 2003). A variety of different
surfaces can be assumed to have been coated by layers of enzymes or mixtures of enzymes may be used, depending
nonionic block copolymer surfactants. on whether the deposits contain substantial amounts of
other materials, such as starch, cellulose, proteins, etc.
Ionic surfactants... It has been found that triglyceride fats often are a main
...are sometimes considered undesirable in industrial contributor to the tacky nature of wood resins during
applications, since their performance is expected to papermaking operations (Fischer, Messner 1992; Blazey
depend on a myriad of other ionic species in the system et al. 2002). It was shown, in the case of unbleached
where they might be applied. Dreisbach and coworkers sulfite pulp, that pitch problems could be minimized by
(1996) showed, however, that it is possible to use a treatment with lipases, followed by alkaline extraction
negatively charged surfactant in combination with a (Fischer, Messner 1992). Though this treatment did not
cationic polymer retention aid. Several authors have remove all of the resinous material from the pulp, the
noted that ionic surfactants can be used effectively to tackiness was greatly reduced. Related enzyme
minimize organic or microbiological deposits (Hassler treatments of mechanical pulp have been shown to reduce
1988; Robertson, Taylor 1994; Abraham 1998). pitch deposits during newsprint production (Skjold-
A renewed interest in surfactant addition of the paper Jørgensen, Lange 1991).
machine wet end has been sparked by findings that some When using esterase enzymes for pitch control, the
of them are effective for control of biofilm deposition levels of carboxylic acid groups in the tacky substances
and growth (Robertson, Taylor 1994; Donlan et al. 2000). will tend to increase. For this reason, it makes sense to
Sessile bacteria, which mainly are found attached as think in terms of combined or sequential additive pro-
continuous colonies on wetted surfaces (Martinelli et al. grams, including highly charged cationic polymers or
2002), tend to be much more relevant for deposit positively charged mineral surfaces.
problems, compared to the suspended bacteria that Proteolytic enzymes provide papermakers with an
usually show up in bacterial counts, using petri dish alternative means for attacking biofilms, both during pro-
techniques. It appears that interactions of the surfactant duction and during shutdowns (Galon 1998). It has been
molecules with cell walls of sessile bacteria can make found that such enzymes can hydrolyze the filaments
them more vulnerable to the effects of certain biocides within bacterial cells that are essential to film formation.
(Donlan et al. 2000). Also, the surfactants may interfere
with the adhesion of bacterial cells and other life functions.
Surface treatments
Solvents So far this review has focused mainly on treatment
Due to the oleophilic nature of the binder materials in strategies involving aqueous suspensions. There are addi-
most tacky deposits it is expected that organic solvents tional deposit-control strategies that involve either inter-
will be effective for cleaning paper machine systems mittent or continuous treatment of solid surfaces within
(Doshi 1992). However, due to concerns about airborne the paper machine system. As described below, these
hydrocarbons (Anastas et al. 2001; Allen 2002), the use strategies include so-called “boilouts” of the system
of organic solvents in paper machine systems is during maintenance shutdowns, selection of construction
becoming less common. Solvents tend to be used during materials that resist deposit formation, and spray-applica-
scheduled shutdowns for removal of especially stubborn tion of chemicals onto periodically wetted elements such
deposits. As mentioned in the context of surfactants, as forming fabrics.
another approach is to make solvents more compatible
with the water phase by forming an emulsion (Dreisbach, Boilouts
Champine 2002). It is a standard practice in paper mills to periodically shut
Kerosene, which is basically a high-boiling mineral down operations and clean the wetted surfaces of a paper
oil, is probably the most commonly used solvent for machine, usually with an emphasis on the short-loop

Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006 165
recirculation system and wet-press section (Glazer 1991; Dreisbach 1998; Aston, Stewart 1991) and aluminum
Guillory 1998; Guillory, Towery 1998). Papermaking salts (Colman et al. 1996) have been used, sometimes in
efficiency and product quality often suffer if too much combination with surfactants.
time elapses between such cleanups (Stitt 1997). The mechanism by which passivation treatments
The term “boilout,” emphasizing the use of elevated appear to work is somewhat counter-intuitive, since
temperatures to clean papermaking equipment, should not cationic polymers and aluminum products might be
be taken literally. Steam is often used for the heating of expected to precipitated negatively charged tacky
solutions used for wash-ups of the short-loop of paper materials onto the equipment surfaces. However, as
machine systems, but temperatures are typically in the proposed by Kenny and Engstrom (1988), results suggest
range of 60-71 oC (Guillory, Towery 1998). A common complexation between adsorbed cationic substances and
practice involves treatment with an alkaline detergent solu- mainly water-loving, negatively charged colloids or poly-
tion, often having a pH in the range of 10-13. However, mers present in the process water. Duffy and Aston
depending on the nature of the deposited materials, acidic (1989) found further support for such a mechanism,
solutions may also be used. In some cases it is possible to noting that forming fabrics developed a tan color during
avoid use of high or low pH solutions by use of enzymes continual treatment, consistent with the build-up of a thin
capable of breaking down the binder materials in a variety layer of hydrophilic material. Nguyen and Dreisbach
of deposits (Anstey et al. 1998). measured the tack force following different kinds of
spray treatments of forming fabrics in intermittent con-
Deposit-incompatible surfaces tact with paper machine process water (1998). Their
Chemical treatments can make it possible to run a paper results were consistent with a reduction in tack force due
machine longer, before operating efficiency begins to to adsorbed hydrophilic materials. To carry the idea one
fall. Another approach is to build the paper machine out step further, it is possible to implement successive spray
of deposit-resistant materials (Kallio, Kekkonen 2005). treatments with cationic and anionic hydrophilic poly-
For example, fluorocarbons can be used in the manu- mers to make surfaces resistant to tacky deposits
facture of forming fabrics (Fischer 1999). Fluorocarbon (Welkener, Hassler 1994).
coverings are commonly used on dryer cans, especially in
the early part of the dryer section on machines using
recovered fibers with high levels of sticky materials Test methods for tacky deposits
(Urbanski 1990). A shortcoming of these materials is a It can be difficult to achieve credible simulations of
relatively low mechanical/surface resistance. They tend to production problems by use of laboratory tests. During
wear out faster as compared to others surfaces within the commercial-scale papermaking it is common for a wetted
paper machine system. Recently, stainless steel materials surface to be exposed to literally tons of materials, with
have become available that resist biological fouling in intense flow conditions and elevated temperatures contin-
food applications (Santos et al. 2004). uing without significant interruption for many days.
A factor that tends to defeat anti-deposit strategies Though papermaking furnish often contains 1-5% of
based on construction materials and polymer compoun- pitch or sticky materials, on a weight basis, the propor-
ding of paper machine clothing is the fact that once depo- tion of this material that ever becomes involved in depo-
sits start to form, the nature of the underlying “clean” sits usually is quite small. However, even a very small
surface may become irrelevant. In the case of pitch amount of these materials, if deposited in a critical
deposits, oleophilic substances already on a surface can location, may be enough to require a shutdown of a paper
provide an attachment point for like materials coming machine system.
from the bulk phase. Imperfections, breaks in a coating,
or abraded areas may provide a beach-head, upon which Coupon tests for in-mill use
deposits may start to build. In addition, there is no con- For the reasons just outlined, gravimetric determinations
struction material that can completely compensate for of deposit amounts usually are limited to full-scale paper
design deficiencies in a paper machine system, such as production. “Coupons,” usually consisting of metal or
dead areas of flow where deposits can settle by gravity. plastic plates, are weighed and then placed so that they
are exposed to steady flow (Dreisbach, Michalopoulos
Cationic spray treatments (passivation) 1989; Pelton, Lawrence 1991). The mass of deposit is
Fabrics used in papermaking are mostly made from determined after a certain time, by drying and weighing.
polymers having relatively low surface energy, and there- Alternatively, the deposited material may be observed
fore they are prone to organic deposition. The word microscopically (Pelton, Lawrence 1991). Coupon
“passivation” is often used when referring to spray treat- surfaces also may be extracted to collect and analyze
ments of these forming fabrics and other surfaces that are soluble materials. Sometimes the coupons are placed in a
intermittently wetted by paper machine furnish or white- side-stream, making it possible to evaluate different
water (Doshi 1992). Many papermakers have observed chemical treatment options.
substantial benefits by applying mist showers that An innovative method for monitoring the build-up of
contained low concentrations of cationic substances in biofilms in a paper machine system uses a transparent
solution (Rendé 1994; Nguyen, Dreisbach 1998). High- disk that rotates while partly submerged in process water
charge-density cationic polymers (Colman et al. 1996; (Flemming et al. 2001). A decrease in light transmission
Kenney, Engstrom 1988; Duffy, Aston 1989; Nguyen, is used to indicate biofilm growth.

166 Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006
Laboratory methods with enhanced deposition Microscopic methods also can be used to look for objects
Many laboratory-oriented methods for evaluation of that have shapes consistent with pitch or stickies.
prospective deposit-control treatments involve different Detailed chemical analysis can be applied effectively,
ways of accelerating the deposition process. One way to not only in examination of deposits, but also to track the
achieve this goal is to apply hydrodynamic shear using an amounts and ratios of different potentially tacky
agitator. Often the best way to quantify the amount of substances in wood, waste paper, or solvent-extracts from
deposit on the tips of impellor blades is by use of a the papermaking process streams. Work by Blazey et al.
solvent, followed by chemical analysis. (2002) showed that the ratio between triglyceride fats and
A more vigorous way to induce deposition of fatty acids in wood pitch can have a very high correlation
suspended tacky particles onto stainless steel employs a to the frequency of deposit problems. Infrared analysis
vibrating coupon (Hassler 1988). The momentum of can quickly show whether a given deposit is predo-
individual tacky particles causes them to impinge upon minantly pitch-derived, rich in synthetic resins, bio-
coupon surfaces. logical, or mainly inorganic.
To evaluate conditions relative to the deposition of
sticky substances onto a plastic fabric, the Pira research Wettability
group developed a system in which fabrics are held in The laboratory-oriented methods discussed up to this
metal frames (Abraham 1998). The frames undergo a point are mainly appropriate for deposit problems that
reciprocating motion, repeatedly drawing the fabric either have already occurred, or there is so much tacky
surfaces through the aqueous sample, such that there is materials present in the system that the listed methods are
flow through the fabric. After a given time, the samples able to achieve statistically significant results. Looking to
may be weighed or microscopically inspected. A later the future, it would be a great advantage to be able to
modification involves additional agitators to accelerate rapidly quantify the initial, trace amounts of resinous
the deposition process (Carré et al. 1998). materials that deposit onto a test surface during a relati-
Given the high affinity of many tacky materials for vely short period of time. Such a method would make it
plastic surfaces, it makes sense to consider the use of more feasible to carry out meaningful tests in the lab
plastic particles as collectors. The plastic particles are with moderate amounts of papermaking furnish, while
weighed before and after exposure to an agitated fiber avoiding the need to “spike” samples with unrealistic
suspension. One such method entails use of plastic foam levels of contaminant. Alternatively, it might then be
as a collector (Ling et al. 1993). Blanco et al. (2000) possible to place a probe into different parts of a running
reported a system for quantifying the deposition onto a paper machine system and obtain prompt feedback about
rotor. Quantification was achieved by weighing or by the initial rate of deposition of tacky materials.
image analysis. In principle, techniques involving measurement of
contact angles on test surfaces are particularly well suited
Direct observation of process water to detection of tacky deposits at their initial stages of
Counts of microscopic particles in a sample of paper formation. Theoretical and experimental studies have
machine water are often used to estimate the likelihood of shown that contact angles sense the outermost molecular
deposit problems (Parmentier 1980b; Winter et al. 1992). layers of surfaces (Fowkes 1965; Shafrin, Zisman 1967;
Due to their fluid nature, pitch particles often can be Good 1973; Morra et al. 1990; Mantel, Wightman 1994;
recognized by their spherical shape. Unfortunately, the Extrand 2004). Based on measured contact angles it is
concentration of suspended pitch particles is not necessari- possible to characterize critical surface tensions of
ly well correlated with the frequency or extent of deposits. various solid surfaces, either clean or contaminated. It is
Rather, the material in suspension tends to be self-selected even possible to detect sub-monolayer quantities of
as the colloidally-stable, deposit-resistant material. deposited material. The main requirement is that the
Recently it has been shown that substantially more can adsorption one wishes to detect must significantly affect
be learned by monitoring colloidal particles in paperma- the wettability of the selected substrate. Related tests
king process water by using spectroscopic analysis at a were carried out by Ling (1993) who measured the
given probing wavelength (Vähäsalo 2005). Temperature contact angles of oil droplets on the immersed surfaces of
conditions leading to sticking collisions among tacky various deposits. In other work the size of bubbles
particles can be revealed by changes in the number attached to immersed surfaces was evaluated as a means
concentrations of suspended particles. By flow cyto- of judging surface energy parameters (Ling 1994).
metry, with appropriate use of surface-specific stains, it
is possible to identify populations of different particulate
components in the whitewater. Closing comments
With so many types of tacky materials, each with its own
Collection and examination of deposit samples range of composition-dependent behaviors, and so many
A whole class of methods can be used to examine either potential interactions between these materials and other
coupons, representing the wetted surfaces of paper- components of a paper machine system, it can be a
making equipment, or samples of deposits collected from challenge to identify the most cost-effective and reliable
paper machines. Stains can reveal aspects of the hydrop- deposit control strategies. As was shown in sections 3 and
hilic, hydrophobic, or charged nature of the deposited 4 of this review, there are a great many different deposit-
material. Bacterial slime can be shown by ATP-type tests. control strategies that might be applied, either individual-

Nordic Pulp and Paper Research Journal Vol 21 no. 2/2006 167
 anionic trash-like pitch, Proc. Papermakers Conf., 535, TAPPI Press, Atlanta.
ly or in various combinations. All of this adds up to a Böhmer, M. R., Evers, O. A., and Scheutjens, J. M. H. M. (1990): Weak poly-
great deal of challenging work, including opportunities electrolytes between two surfaces: adsorption and stabilization, Macromolecules,
for the next generation of papermaking technologists and 23(8), 2288.
Borchardt, J. K. (1992): Chemical structure – property relationships of deinking
scientists.
surfactants, Prog. Paper Recycling, 1 (2): 45-60 (1992).
Fortunately, as documented in the literature cited here,
Bottéro, J. Y., Cases, J. M., Flessinger, F., and Poirier, J. E. (1980): Studies of
substantial progress has been achieved with respect to the hydrolyzed aluminum chloride solutions. 1. Nature of aluminum species and com-
organic chemistry, colloidal stability, tacky charac- position of aqueous solutions, J. Phys. Chem. 84(22), 2933.
teristics, and analytical detection of substances tending to Bottéro, J.-Y., and Fiessinger, F. (1989): Aluminum chemistry in aqueous solu-
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new treatment strategies to fight tacky deposits have been Bouffard, S. C., and Duff, S. J. B. (1999): White water treatment using organi-
developed, and it can be expected that the pace of such cally tailored heulandite minerals, Tappi, 82(7), 178.
innovations will continue. Of the various barriers that Braitberg, L. D. (1966): Controlling pitch accumulations in paper mill systems,
tend to stand in the way of prompt, cost-effective Tappi, 49(11), 128A.
resolution of tacky deposit issues, one of the most critical Brink, M. W. (1997): Recycled Fiber Use vs. Paper Machine Runnability – You
Can Win!, Proc. Eng. Papermakers Conf., 51, TAPPI Press, Atlanta.
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Buzby, J. H., and Evans, R. D. (1991): Method for controlling pitch deposits in
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pulp and papermaking processes with organotitanium (IV) compound, US pat.
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Ultra-sensitive methods, such as those based on wetta- Capozzi, A. M., and Rendé, D. S. (1994): Particle management: An effective
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Tappi, 39(10), 684.

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