WET END CHEMISTRY

What is Wet End Chemistry?

The interactions between all the components in the papermaking

system:
 Surface/Interfacial
 Ionic
 Colloidal
What is Wet End Chemistry?

 “All the things you don’t see -

that affect the things you do see!”
Why Is It Important?
 Achievement of Paper Properties
 Structural - formation
 Mechanical - strength
 Appearance - optical
 Barrier & Resistance - sizing
 Permanence - stability

 Enhancement of Runnability
 Machine Efficiency
 Drainage - speed
 Foaming
 Spots, Holes & Deposits

Wet End Chemistry

 Materials
 Types
 Characteristics

 Principles
 Surface Area
 Conductivity
 Electrostatic Charge
 Coagulation & Flocculation
What are the Different Materials?
 Water
 Dissolved Electrolytes
 Suspended Fibers
 Suspended Fiber Fines
 Suspended Filler Particles
 Surface-active Molecules (alone or as aggregates,
i.e. detergents, dispersants, wood extractives, defoamers)
 Dissolved Polyelectrolytes - i.e. PAM, cationic starch
wet and dry strength resins
  Aggregated Sizing Molecules

Size & Shape of Papermaking Components

 Tremendous Variation

 Fibers: 10-50 microns by 1-7 mm long

 Fines: < 1 micron wide by <76 microns long
 Filler: 0.1-10 microns
 ASA Size: < 1 micron
 Colloidal Silica: < 0.01 microns

Characteristics of Fiber & Fines

 Composition

 Surface Area

 Charge/pH Effects

 Ion Exchange
Characteristics of Fiber & Fines
 Bleached Kraft Fibers:
 Most Lignin is Removed
 Most “Pitch” is Removed

 Groundwood Fibers:
 Lignin Remains
 “Pitch” Remains
Characteristics of Fiber & Fines
 Pitch, Lignin & Cellulose contain Carboxyl Groups

 Lignin also contains Phenolic OH Groups

 Sulfite Pulps also contain Sulfonic Acid Groups

Carboxyl & Sulfonic Acid Groups
Characteristics of Fiber & Fines
 All Groups Ionize and
Become Anionic In Water

 Ionization is pH Dependent
 As pH Increases from 3 to 7, carboxyl groups on cellulose, pitch, and lignin become
more anionic.
 Above pH 8, phenolic OH groups also begin to contribute to anionic charge.
Characteristics of Fiber & Fines
 The amount of anionic charge on fiber and fines has multiple effects:
 Retention of Additives
 Dewatering Rate
 Formation
 Sizing
 Effectiveness of Retention Aids
Characteristics of Fiber & Fines
 Surface Area:
 410 CSF Pulp 2.1 m2/g
 Fiber Fraction 1.2 m2/g
 Fines Fraction (16.5%) 8.0 m2/g
Characteristics of Fiber & Fines
 Surface Area:
 Surface Area of Fines is Much Greater than Fiber
 Many Chemical Additives will adsorb Preferentially onto Fines
Characteristics of Fiber & Fines
 Retention of the Fines Fraction of a Furnishis CRITICAL to the Effectiveness of Wet
End additives :
 Size
 Die, FWA
 Wet End Stark
 Wet/Dry Stretch Retins
Non-Fiber Materials
 Dissolved
 Sulfates, chlorides, oxalates, acetates
 Derived from:
 Pulp
 Bleach plant carryover
 Water Source

 Effects:
 Increased Scale Deposits
 Increased Conductivity
 Reduced Effectiveness of some Additives
Non-Fiber Materials
 Dissolved
 Sulfates, chlorides, oxalates, acetates
 Derived from:
 Pulp
 Bleach plant carryover
 Water Source

 Effects:
 Increased Scale Deposits
 Increased Conductivity
 Reduced Effectiveness of some Additives
Non-Fiber Materials
 Colloids
 Dispersions of particles that are too small
to settle out (<1 micron)

 Hydrophilic
 Hydrophobic
Hydrophilic & Hydrophobic Papermaking Materials
 Hydrophilic - “water loving”
 Stark dissolved in water
 Hemicellulose dissolved in water
 Surfactants, dispersants, wetting agents
dissolved in water
 Retention aids dissolved in water

 Hydrophobic - “water fearing”

 All pigments dispersed in water
 Fines dispersed in water
 Rosin size dispersed in water
 Wood Pitch dispersed in water
Colloidal Materials
 Need to be retained!
 Desired Additives
 “Interfering Substances” (Pitch, Stickies)

 Otherwise:
 Build up in Whitewater System
 Cause Deposits, Spots, Breaks
Colloidal Materials
 Don’t want to be Retained!
 Most are hydrophobic
 don’t like fiber
 Have a net anionic charge
 don’t like each other
 Too small for mechanical retention
Influence of Particle Size onFiller Retention
Mechanisms for the Aggregation of Hydrophobic Colloidal Suspensions
 Coagulation
The destabilization of a colloidal suspension by compression of the
electrical double layer with salts or polyelectrolytes. A charge
neutralization phenomenon involving the reduction of Zeta Potential to a
point where Van der Waals attractive forces predominate.

What is Charge?
 Practically all materials in a papermaking furnish possess an electrostatic charge at
their interface with water.
 Charge is almost always anionic
 Largely responsible for the dispersed nature of most colloids
Charge
 Zeta Potential
 the electrical potential at the point where the Stern & Diffuse layers meet
 Degree of Repulsion
 determined by the thickness of the doublelayer or “cloud”

Coagulation
 Coagulated materials are sensitive to shear
  Multivalent cations are more effective
coagulants than monovalent cations

 Al+3 >>> Ca+2 >> Na+1

 Polyelectrolytes are more effective than simple electrolytes

 polyamine > alum
Mechanisms for the Aggregation of Hydrophobic Colloidal Suspensions
 Coagulation - The destabilization of a colloidal suspension by compression of the
electrical double layer with salts or polyelectrolytes. A charge neutralization phenomenon
involving the reduction of Zeta Potential to a point where Van der Waals attractive forces
predominate.
 Flocculation - The destabilization of a colloidal suspension by bonding the particle
together, usually with a polymeric flocculant.
Flocculation
 Patch Flocculation
 Bridge Flocculation
 “Un-Flocculation”
Patch Flocculation
 Usually accompli shed with low molecular weight cation polyelectrolytes
 Much faster aggregation rate than coagulation with simple electrolytes
 Shear sensitive
 aggregates re-form after shear removed
 “soft-floc”

Bridging Flocculation
 Accomplished with high molecular
weight polymers
 Highly influenced by molecular weight and charge density of polymer
 Forms larger flocs
 Aggregates tend to reform as patch (soft) flocs when sheared
Hard Floc Behavior
The Two Can Be Combined
Dual Polymer System
Steric Stabilization
Factors Affecting Polymer Adsorption
 Polymer Characteristics - charge density, molecular weight, chain length, backbone
conformation, flexibility

 Particle Characteristics - available adsorption sites, surface area, surface charge

 Physical Environment - shear and turbulence, furnish consistency, order of addition

 Chemical Environment - pH, conductivity, “interfering substances”

Interfering Substances
 Fresh Water
 Calcium and Magnesium hardness
 Organic Matter
 Residual Chlorine
 Suspended solids

 Pulping Residuals
 Sodium salts
 Rosin soaps
 Fatty acid soaps
 Lignin compounds
Interfering Substances
 Bleaching Residuals
 Sodium salts
 Calcium salts from Calcium hypochlorite
 Alkali-soluble cellulose and hemicellulose
 Broke
 Stark
 Adhesives
 Inks
 Coating Components
Interfering Substances (Conductivity)
 Conductivity
 Measurement of dissolved ions
 Many “interfering substances” are soluble ionized materials
High levels = High Conductivity
High Conductivity = Bad News
Conductivity of Interfering Substances
 Reduces Charge on Particles
 Reduces Affinity for Charged Polymers
 Causes “Coiling” of Polymer Molecule
 Reduces Efficiency of Polymer
Interfering Substances (Charge)
 Charge
 Most colloidal “interfering substances”are anionic
 “Anionic Trash”---- High Amounts = Bad News
Charge of Interfering Substances
 Increases Cationic Demand
 Competes with desired materials for interaction with cationic polymers
 Neutralizes cationic charge on polymers
 reduces efficiency
 Adsorbs onto bentonite
 Acts as a dispersant
Charge Measurement
 More complex than measuring conductivity
 2 Most Popular Methods
 Microelectrophoresis
 A.C. Streaming Current
Charge Measurement
 Microelectrophoresis
 Used to determine Zeta Potential
 Measures Intensity of Charge
 Well defined
 A.C. Streaming Current
 Used by Mutek and Chemtrac meters
 Measures intensity of Charge, but...
 not Zeta Potential
 highly affected by conductivity
 poorly reproducible
A.C. Streaming Current
 Used for endpoint indicator in charge titration
 Charge titration measures amount of charge
 Only equal to Zeta Potential at “0” millivolt reading
A.C. Streaming Current - Why Use It?
 Determine charge density of pulps, furnish and traywater
 Estimate Coagulant Addition
 Determine a change in the charge density of pulps, furnish and traywater
 Determine the source of a change:
 poor kraft pulp washing
 broke addition changes
 deink plant carryover
 Alcofix feed pump failure

Wet End Chemistry

The enhancement of retention and drainage control of the papermaking system through
understanding of the physical and chemical characteristics of papermaking components
for the achievement of desired paper properties and improved papermachine runnability.