2012 Polymers anc colloids in papermaking

Chemical state of the wet end

Trends in papermaking
Chemical problems in papermaking
Key parameters in controlling the chemistry in
papermaking

Challenges of papermaking for

paper chemistry
Trends:

− Lowering the grammage

− Increase of filler content
− High machine speeds
− Twin wire machines Why?
− Coating, bleaching, use of deinked pulp Effects?
− Higher pH (neutral, alkaline)
− Closure of water circuits

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2012 Polymers anc colloids in papermaking

Trends in papermaking -
share of wet end chemistry
− Lowering the grammage
− Retention
− Formation
− Strength properties and opacity
− Penetration of the coating colour into the base paper
− Use of fillers
− Papre quality, cost savings
− Strength properties – two sideness
− retention

Trends in papermaking -
share of wet end chemistry
− High machine speed and twin wire machines
− Turbulent flows – decreased retention
− Fast and vigorous drainage
− Retention and drainage

− Coating (especially wood containing grades)

− Coated broke
− Depositions (”white pitch”)
− Usage of additives (fixing agents, adsorbents)
− Importance of analyzes

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2012 Polymers anc colloids in papermaking

Trends in papermaking -
share of wet end chemistry
− Increased bleaching
− Bleaching chemicals
− Release of dissolved and colloidal sublstances from pulp
− Neutral process (especially wood containing grades)
− Depositions
− Pitch control
− Requirements for analysis
− Closure of water circulation system
− Enrichment of DCS in circulation water
− Depositions, foaming, runnabillity and quality problems, poor
effective of additives, increased concumption of additives
− Use of chemicals, internal purification

Higher pH (neutral/alkaline)

Advantages and disadvantages of neutral/alkaline process

Advantages: Disadvantages:
− CaCO3 as filler − Synthetic hydrophoby sizes –
− Lower energy consumption hydrolyzation of sizes
(beating, drying) − Acidic pulps can couse problems
− Better drainage, drying (integrated mills)
− Lower amount of inorganic − High amount of anionic
dissolved surbstances from mechanical
substances pulp
− Reduction of fresh water usage − Deposition
p p
problems
− Cheaper raw materials − Microbiological activity – slime
problems
− Less corrosion
− Choice of chemicals

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2012 Polymers anc colloids in papermaking

Higher pH (neutral/alkaline)

Advantages and disadvantages of neutral/alkaline process (product)

Advantages:
− Better strength properties –
possible to increase the filler content
− Better opacity
− Good printability
(porosity, bulk, brightness,…)
− Better archiving stability
Disadvantages:
− Difficult to control the sizing
degree
− Size reversion is possible
− Yellowing of maechanical pulp
− Paper slipperiness

Closure of water circulation system

− Functions of water circulation system

− Enables to effective reuse of the process water
− Better material economy
− Better distribution of fines in the product

− Criteria for good functionality

− Contollability
− Stability
− Material economy
− Cleansing
− Fresh water concumption
− Heat economy
− Investment costs
− Fluency of chemical feeding

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2012 Polymers anc colloids in papermaking

Closure of water circulation system

Advantages: Disadvantages:
− Technical: − Enrichment of detrimental
− Lower demand for water treatment substances in circulation water
− Better drainage − Product quality
− Runnability
− Economical: − Effect on the function of the
− Lower water and waste water process chemicals
treatment costs
− Lower fiber and filler loss − Increased electrolyte
− Lower operating costs concentration
− C
Corrosion
i
− Environmental: − Effect on the function of the
− Energy savings process chemicals
− Water savings − Increased temperature
− Less effluents − Dissolving
− Micro-organisms

Chemical problems in paper

making
Problem types
Control of chemistry

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2012 Polymers anc colloids in papermaking

Chemical problem types in paper

making
− Basicly two types

− Retention problem of some components

− Uncontrollable phase transitions

Chemical problems in paper making

Uncontrollable phase transitions

− From dissolved to solid
− Solubility of substances
− Temperature, pH, electrolyte concentration
− Molecular weight
− Concentration

− Increase of particle size in dispersion

− Stability of the colloidal system
− temperature, pH, electrolyte concentration
− System charge

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2012 Polymers anc colloids in papermaking

Controlling the chemistry in

papermaking process
− Controlling the chemistry by using chemicals
− Introduction of new chemicals
Ö unnecessary use of chemicals?

− Controlling the chemistry by chemical kkey factors

− Temperature, pH, electrolyte concentration
− charge
− Amount of dissolved and colloidal substances
− Gas content
Ö Decreased demand for chemical use

Key parameters
Temperature
pH
Conductivity
Gas content
Amount of dissolved and colloidal substances
Charge

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2012 Polymers anc colloids in papermaking

Temperature

Temperature

− Dissolving of wood material

− Pulping
p g
− Higher temperatures
Increased amount of dissolved and
− More violent conditions Ö dispersed substances in water phase

− Paper making
− Increased temperature Ö increased amount of dissolved substances
− Decreased temperature Ö depositions
− Conditioning of temperat
temperature
re is important!

− Affecting factors
− Breaks and downtimes
− Need of extra fresh water

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2012 Polymers anc colloids in papermaking

pH

pH

− pH have effect on
− Charge
− Dissolving of wood material
− The pH adjustment affects slowly
− pH-adjusment chemical must enter into the fiber
− Importance of measuring point
− Sudden changes in pH
− Precipitation of dissolved and colloidal substances

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2012 Polymers anc colloids in papermaking

pH – Effect on the use of

polyelectrolytes
• pH have effect on the dissosiation equilibrium of charged groups in the
polyelectrolyte
• Each retention aid acts at certail pH region
• Tertiary aminegroup loses its cationicity at high pH
• Quaternary aminegroup: charge almost unchanged at large pH range
(papermaking pH 4 – 9)

• The protonisation of acid groups in fiber and fines at low pH Ö decreased

anionic charge

• Increased pH – usually higher amount of polyelectrolyte is needed

• Derives from the change of ionic strength

Conductivity

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2012 Polymers anc colloids in papermaking

Conductivity

− Derives from dissolved inorganic substances

− Sodium and sulphur compounds
− Calcium
− Aluminium
− Polyvalent cations (Ca, Al, Fe)
− Have effect on phase changes of dissolved and dispersed dsubstances

− Crirical coagulation concentration

− For example increase of Ca-concentration

Critical coagulation concentration (Cc)

AH a 2c0
V tot = V rep + V attr = 2πε 0 ε r a φ d e −κx − κ = ze0
2

12 x kTε 0ε r

If the energy barrier is decreased so that Vtot = 0, occurs rapid coagulation.

Approximations for required electrolyte concentration for coagulation (Schultze-Hardyn
rule):
1 1 φ4 1
cc = k1 ≈ k2 cc = k 3 2
≈ k4
AH z
2 6
z6 AH z 2
z2
when φd > 100 mV when φd < 25 mV

Critical coagulation concentration is the electrolyte concentration at which the maximum

of interaction energy = 0. In other words, the lowest electrolyte concentration, which is
required for rapid coagulation of colloid.

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2012 Polymers anc colloids in papermaking

Coagulation with electrolyte

Critical coagulation concentration

Theory Na+ Ba2+ La3+

high φd 1/z6 1 1/64 1/729
cc=k2*1/z6 Ratio of cc:cc(La3+) 729 11,4 1
low φd 1/z2 1 1/4 1/9
cc=k4*1/z2 Ratio of cc:cc(La3+) 9 2,25 1
Results from
laboratory mmol/dm3 750 27 1,3
experiments
Ratio of cc:cc(La3+) 573 20,5 1

Conductivity – effect on the use of

polyelectrolytes
− The ionic strength has effect on the behaviour of polyelectrolyte molecul
− Repulsion between the charges in the molecul chain
Ö chain straightens
− High ionic strength ”shades” the repulsive forces
Ö conformation change of polyelectrolyte molecul in solution
− No effect if the charge density of the polyelectrolyte is low

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2012 Polymers anc colloids in papermaking

Gas content

Gas content

− Air, carbon dioxide (CaCO3)

− Forming of interfaces
− Adsorption of surface active agent on the interfaces
− Pinholes, defects, breaks
− Concistency measurement
− Gas deteriotes concistency gas measurement
− Effect on automatic retention control

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2012 Polymers anc colloids in papermaking

Dissolved organic substances

Dissolved organic substances

− Depends on the raw material

− From chemical pulp dissolves < 0,5 %
− Mechanical pulp 2 – 5 %

− Dissolved organic substances from mechanical pulp

− In the same forum as in wood
− Extractives (pitch)

− Chemical pulp
− Dissolved sugars and hemicelluloses

− Starch used as additive

− Used process chemicals

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2012 Polymers anc colloids in papermaking

Disturbing substances

− Dissolved and colloidal substances which have negative effect on

retention and drainage and/or runnability
− Inorganic and low molecular weight salts

− Dissolved (anionic) organic substances

− (anionic) colloidal substances

Disturbing substances

− Amount of disturbing substances

depends on
ount
Disturbing substances, % of coming amo

− Raw materials adsorption

d ti

− additives
− Use of fresh water
− Adsorption on surfaces of fibers
and fines – at low concentrations
high adsorption
− Solubility of substances – at higer
concentration levels
agglomeration

Amount of waste water, %

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2012 Polymers anc colloids in papermaking

Disturbing substances

− Remarkable part of DCS are anionic

− From mechanical pulp
− Alkaline circumstances of peroxide bleaching
− From refining, deinked pulp, coated broke, additives,…
− Interactions with retention chemicals

− In anionic circumstances particles of anionic disturbing substances

(hydrophobic colloids) repel eatch others – stabile colloid
− Loss of stability (DLVO-theory)
− Uncontrollably because caused by some physical, chemical or machnical factor
Ö disturbing effects

Disturbing substances

− Problems caused by detrimental substances

− Depositions ja unwanted reactions of disturbing substances in different locations
of water circulation system
− contamination of machine parts
− stickies
− Breaks, pinholes etc.
− Quality defects and decreased runnability
− Decreased effciency of additives (retention aids, internal sizes, …)
− Part of the dosed additives get into the water circulation, where they act as
disturbing substances

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2012 Polymers anc colloids in papermaking

Interactions of polyelectrolytes

Retention in system containg high amount

of disturbing substances

− High amount of aniionic substances

− Concumption of retention aids
− Low efficiency of retention aids
− More complicated retention aid systems are required
− Possibilities
− Eliminating the disturbing substances from raw material (washing of pulp)
− Selection of the retention aid system
− Use of additives for treatment of disturbing substances
− Adsorbents
− Coagulants
g
− Use of enzymes
− pectinase, lipase etc.

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2012 Polymers anc colloids in papermaking

Retention aid systems for systems containing

high amount of disturbing substances

System Mechanism
anionic PAM + bentonite Network formation
PEO + phenol resin Network formation
Coagulant + cationic PAM Charge neutralization + bridging

adsorbent + cationic PAM adsorption + bridging

Charge

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2012 Polymers anc colloids in papermaking

Sources of charge in papermaking

• solids
• Fibers, fillers
• Low anionic charge
• Dissolved and colloidal substances (DCS)
• ”Anionic trash”
• High anionic charge
• Additives
• Coagulants – high cationic charge
• Retention aids – low cationic charge
• Importance
• R t ti
Retention
• Colloidal stability
• Depositions
• Fixation of disturbing substances on the web

Factors affecting charge

• Decreased fresh water concumption

• Increased concentration of dissolved and colloidal substances
• Controllability
C t ll bilit andd runnability
bilit off th
the process

• Use of chemicals (fixatives, coagulants)

• Aim to neutralize the charge
• Unstable state (colloidal stability)

• Charge control is rquired for retention control

• High amounts of fillers
• Coated brokse
• Components dissolved from wood

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2012 Polymers anc colloids in papermaking

Wet end analysis

Charge
Retention
On-line analysis

State of wet end

Multivalent
cations

Gas Critical threshold

pH
(air, Co2) values?
• on-line
”stability factor”
measurements
(and adjustment)
COD, DOC,
temperature • state during good
TOC, TC
runnabilitytila hyvän
charge, ajettavuuden aikana?
surface charge

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2012 Polymers anc colloids in papermaking

Charcaterization of colloidal state

• Charge measurement
• Turbidityy measurement
• Potentiometric and conductometric titration
• Determination of surface active agents
• Particle size measurement
• Zetapotential

Particles in a papermaking furnish

- ---
-

Filler Cationic additives

Anionic DCS ”anionic trash”

Fibers and fines

− Discreate particles − Dissolved molecules

Ö Surface charge Ö Dissolved charge
− Mineral pigments and fillers − Anionic trash
− Chemical additives

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2012 Polymers anc colloids in papermaking

Two diffierent measurements describing

charge

− Zetapotential
− Defines the adsorption capacity of the particle (fiber, fines, filler)
− Indicates adsorption of additives on the particle surface
− Cationic demand
− Solid + DCS or only DCS (filtrated sample)
− Can be measured
− Amount of anionic DCS (anionic trash)
− Charge of the additives
− Required dosage of fixative

Determination of surface charge of

colloid
− Charge ensues from interactions
between particles and ions in
di
dispersion
i
− Electrostatic forces between particles
determine the colloidal
stability/coagulation
− The amount of charge bound on the
surface depends on chemical balance
(balance of dissociable groups)

− The colloidal stability can be affected by using additives having

effect on surface charges

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2012 Polymers anc colloids in papermaking

Measuring of charge:
Solids, zetapotential

Surface charge
(Zetapotential)

Electrophoresis Streaming potential

P1

v - -- P2
-- -
+ v - -- -
v - -- -- -
-- -
Electomagnetic field causes Moving liquid (water) causes
particles to move electromagnetic field

Measured from very dilute No dilution required, can be

suspensions, thus less useful measured directly from fiber
for papermaking process suspension, head box sample
etc.

Measuring of zetapotential (Electophoresis)

− Electrophoresis
p means the
motion of charged particles in
relation to stationar liquid
phase caused by potential
gradient

Zetapotential is calculated from Smoluchowsk´s − The electric field between two

equation
where
ζ zetapotential
η viscosity of the liquid
ε dielectric constant of the liquid
ν velocity of the particle
E Strength of the electric field
electrodes causes motion of
chardeg particles
− By following the motion of
particles electrophoretic
motion can be determined
(mm/s/V/cm).

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2012 Polymers anc colloids in papermaking

Measuring of zetapotential
(streaming potential)
− Suspension flow is forced to flow
through wire electrode, thus
causing porous plug between the
electrodes
− The charge in mobile electric
double layer moves with the flow
to the electrode causing electric
field
− In balanced state the potential
difference between the − Zetapotential is calculated from
eleoctrodes is measured streaming potentioal
potentioal, pressure
(streaming potential). difference through the plug and
liquid properties
− The charged dissolved and
colloidal substances have not
effect on the streaming potential.

Detemination of the charge

Solids, zetapotential

− Measured zeta-potential is a relative quantity

− Affecting factors
− Electrolyte concentration and valency of ions
− pH
− temperature

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2012 Polymers anc colloids in papermaking

Determination of charge -
DCS (+ solid)
− Polyelectrolyte titration (Colloid titration)
− Measures cationic demand
− The sample is titrated with cationic polyelectrolyte having low molecular weight
until the indicative zetapotential is zero
− The end point can be detected by using
− Indicator or
− Particle Charge Detector, PCD (Streaming current)

The test cell and the displacement

piston of the measuring cell are
made from very hydrophobic
material (PTFE).
Charged macromolecules and
particles adsorbs on the surfaces of
them by van der Waals forces

Mütek PCD

Determination of the cationic demand

(Streaming Current Detector)

− The streaming current detector measures the current caused by streaming

potential in closed circuit
p

a) Stationary dispersion
1: adsorbed particle with
symmetric counter ion layer
2: non-adsorbed particle with
symmetric counter ion layer
b) Flowing fluid
1: adsorbed particle with
“cutted” counter ion layer
y
2: non-adsorbed particle
with symmetric counter ion
− Reciprocating motion of the piston forces the dispersion layer
or liquid flow rapidly along the measuring cell wall
causing the diffuse layer of adsorbed particles to cut

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2012 Polymers anc colloids in papermaking

PCD-signal and zetapotential

− Theoretic correlation
SIP = k * ζ * e (1)
Where
SIP potential caused by flow
k coefficient
e dielectric constant

− The coefficient k includes

− Effects of PCD-equipment on the signal level
− Effect of chemical properties of the sample on the signal level
> Not constant at each measurement
> PCD can not be used as ζ –potential indicator

Cationic demand caused by

solids and DCS

Total demand
total cationic demand = DCS + solids

Solid DCS

− Sample D (dilution) D titration with standard polyelectrolyte

D total cationic demand
− Sample D Removal of solids (filtration, sentrifucation) D titration with standard
polyelectrolyte
D cationic demand of dissolved and colloidal substances
− Cationic demand of solids = total demand – cationic demand of DCS

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2012 Polymers anc colloids in papermaking

Applications

− Measuring of
− Charge of dissolved and colloidal substances
− Surface charge of very small particles about up to 200 µm (latex, pigments,
fillers, fibers and fines
− Amount of anionic dissolved substances
− Functionality of additives (adsorption)

− Small particles have not enough interactions with the surface, thus they
have no effect on electrokinetic phenomenon
− In conductivity measurement all charged material is noticed

Measurement of zetapotential and

CD in process
− The functionality of chemical dosing can be detectec by measuring
zetapotential and CD before and after chemical addition

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2012 Polymers anc colloids in papermaking

Measurement of zetapotential and CD in

process
For example: Succesful functionality of chemical addition can be detected by
following menas

− Addition of cationic starch − Additon of fixing agent (anionic trash catcher,

− Zetapotential decreases
− CD remain constant
D Means that the starch is adsorbed
on the fiber, not reacted with
anionic DCS
catcher
ATC)
− CD decreases
− Zetapotential remains almost constant
D Means that the fixing agent has reactied
with anionic disturbing substances (and
fixed it on the fiber)

starch
t h

Unwanted reaction

starch

Succesfull starch addition

On-line measurements in wet end

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2012 Polymers anc colloids in papermaking

Chemical measurements of papermaking

process

− Easy to measure − Many of them can also be

− temperature measured on-line
− pH − Required amount off
− conductivity
measurents is depent on
− Raw materials
− Amount of dissolved organic material
− product
− turbidity
− process
− Amount of aluminium, calcium and other
multi valent ions
− Gas (air) content
− Starch in the water
ater phase
− charge
− Amount of extractives (pitch)

On-line measurement

− Measuring frequency
− Analyzing time
− Long analyzing time Öless measurements
− Washing
− Washing requirements Ö less measurements
− Sample preservability
− Representative sample collecting
− Decreased amount of sources of error
− Detecting fault situations immediately

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2012 Polymers anc colloids in papermaking

Continuous measuring and control

For example WIC 100 from Raisio Chemicals

(nowadays ABB Industries)
− A complete wet end information system for
paper and board machines
− simultaneously measures chemical and
physical parameters
− Measurements can be transferred
− as trend data directly to the operators
− as processed data directly to control
the process
− Benefits include
− improved production rates
− more uniform paper and board quality
− savings on raw materials, chemicals,
and energy
Wet-End Information Control (WIC)

Wet end (chemistry) on-line

analysis
− Concistency − Certain inorganic and organic
cations
− Flow
− Starch
− Freeness
− COD and TOC
− Fiber length − Charge
− Gas (air) content − Zetapotential
− Temperature − Streamingpotential
− pH − Cationic demand
− Colloid titration
− Conductivity

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2012 Polymers anc colloids in papermaking

Measuring and control of retention on

paper machine

− Retention is determined from concistences in head box and wire pit

− Total and fillerretention are measured separately
− Laboratory measurements:
− Concistency and retention measurements 2-3 times per day
− Variations are not necceccary noticed
− On-line measurement with high frequency
− Information is immediately on hand
− For example fault situations can be noticed immediately

31