Genealogical Tree of the Wet End Chemistry

logging barking
sieving chipping
cooking washing
bleaching straining General Colloid&Surface
Surface
Chemistry Chemistry Science

RETENTION AND FORMATION IN PAPERMAKING

Dr Boris Zhmud, Sveacon Consulting

Hydrodynamics Papermaking Mechanics

wet pressing
Technology
drying calendering

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Papermaking Formation Viewed as Filtration

Drainage is:
- The process of straining the dilute suspension of fibers through the wire.
Formation is:
- The build-up of a coherent web from fibers retained on the wire during
the straining. stock

1. The stock (1-10 g/kg solids, 6 to 18 mm layer thickness) gets on the wire.
pressure

2. Drainage is assisted by foils (upto ~ 20 g/kg) and then by suction boxes. filter cake
drop

(paper web)
3. The formed web leaves the "couch" at 100-200 g/kg solids.
wire
(1) (2) (3)
Dandy
Forming Couch formed filtrate
table roll
head box roll web

Banks of foils suction boxes

Tray Tray
polyester
woven felt
Rate of the Process = Pressure Drop x Filter Cake Permeability
The elements of a Fourdrinier wire part
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Origin of the Pressure Drop Origin of the Pressure Drop (Revisited)

h
ω v
inertial effect
gravitational effect (dominant)
(negligible) r
the underpressure zone
( p = r gh → 0) (the highest velocity)

Streamlines change their direction in the nip between the table roll and the wire, ∂v 1
Euler equation: + ( v ⋅∇) v = − ∇p
v(t) ∂t r
v2
Dv = v(t + Dt ) − v(t ) = rw 2 Dt = Dt
v(t +Δt) r
Δv
Dv v2 r v2
r F =m = r Sh p+ = const
Dt r Bernoulli equation:
r 2
F h p - pressure
ω p = = r v2 v - velocity
S r ω - angular velocity In the nip between the roll and the wire, water moves together with the confining surfaces.
ρ - density Hence, the steamlines shown are identical to the streamlines of an inviscid fluid.
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g - acceleration of gravity www.sveacon.se

1
 Pressure Profile in the Nip Filter Cake Permeability
Table Roll vs. Foil

high medium low

The Kozeny-Carman equation:

(1 − C )3 ∇p
Rate of Dranage = const
S 2C 2 h
Advantages of foils:
C - volume fraction of solids
¾ No speed limits S - specific surface area of solids (10-50 cm2/g)
¾ More sustained low-amplitude pressure profile η - viscosity of liquid
¾ Customized drainage profile
∇p - pressure drop
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Physics Behind the Kozeny-Carman Equation Some Preliminary Remarks

Poiseuille equation for the flow in a cylindrical tube:
The process of forming the web of paper may be represented as
R2 Ê r 2 ˆ —p
vz (r ) = 1- 2 ˜ an example of the unit operation of solid/liquid separation by filtration.
4 ÁË
r
2R R ¯ h
z It proceeds at a rate which is approximately proportional to the pressure
p —p 4
R

Q = 2p Ú r v z (r )dr = R drop and inversely proportional to the basis weight already formed.
0
8 h
As is often the case, the progress of technology in the field of papermaking
2 2 overtakes the need for detailed understanding of the original process.
Ê aˆ Ê aˆ a
S0 = a ; S1 = Á ˜ ; S2 = Á 2 ˜ ; ...
2
a 22
Ë 2¯ Ë2 ¯ S3
Theoretical models more complex than those presented are legion but
2
a2 S0 S2 are of limited use because of the process complexity, e.g.:
Sn = 2n = 2n a
2 2
S2 - the fibres are non-uniform in size and shape;
Q = 22 n Qn μ 22 n Sn2 μ 20n S1
- the flow is not laminar;
2 - the web is not incompressible;
Q - plus many other unaccountable/stochastic factors.
μ S n ¥ P (pores are empty) ¥ P(pores are interconnected)
S  
  

0 1-f (1-f ) 2
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Web Structure Building Characterization of the Fibre Orientation

Fibre Orientation
Using the Polar Diagram

Velocity profile near the slice wall Velocity profile near

and in the jet impact point the drainage line. r(ϕ)
ϕ

Fibres are aligned parallel to the machine ϕ

direction in the slice, in the jet impact point
and on the drainage elements; the overall
felt motion plays no role here.
-90o 0 90o
The preferential orientation of fibres causes The number of intersections with
the "grain" (i.e. the anisotropy of the r(ϕ) ~ number of fibres aligned
the scanning line is counted.
mechanical properties of paper). at a given angle
Templating (combing-out) effect.

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2
 "Rolling" Flocs In-Plane Non-Uniformity

gravity gravity
v(z) wave wave

stock speed

wire speed
machine
Flocs getting a torque due to an excessive jet/wire speed ratio direction

N.B. Bizarre terminology:

"Formation" or "Look-Through" is the visual inspection of the web of paper for “Light edges” due to the gravity wave spreading outwards on the wire table.
small-scale non-uniformity. It is not the same as the "mass density distribution".
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Fibre Flocculation The Concept of a Coherent Fibre Network

Flocculation is the formation of relatively dense aggregates, or "flocs", of fibres.

Flocculation is the most important cause of uneven distribution of basis weight.

A fibre may only become a part

Mason's (mechanistic) theory (1954):
of a network if it is in contact with
Flocculation is viewed as a result of mechanical entanglement of fibres. at least three other fibres

+ doublet, triplet, etc.

2
3⎛d ⎞
Critical concentration by Mason: C ⎜ ⎟ << the real value 2
2⎝ L⎠ ⎛d⎞
Critical concentration by Wahren: C  108p ⎜ ⎟ (good agreement)
d - diameter; L - length
⎝ L⎠

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The Effect of Surface Forces on Flocculation Controlled Flocculation

Controlled flocculation means that flocs can be easily broken without impairing
It is clearly an oversimplification to attribute the formation of flocs retention
merely to the action of locked-in fibres straining against each other,
and to disregard the contribution of adhesion and frictional forces Flocculation of the stock
at points of contact between fibres. cannot be avoided. Retention
agents promote flocculation.
Floc Persistence

(B.Radvan, "Forming the Web of Paper", in the Handbook of Paper Science, 1980)

Rather than attempting to

prevent it, the efforts should
Overflocculation ⇒ bad formation
instead be aimed at providing
and uneven sheet
conditions for dispersing
flocs.

Remedies: High shear (use of

shear-thickening agents), small 1 10 100 η [cP]
No flocculation ⇒ poor retention turbulence, shaking the wire.
Fluid Viscosity

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3
 Relation between the Polymer Adsorption
Common Flocculation Mechanisms and Flocculation Efficiency
1. Patch Flocculation Flocculation
2. Bridging Flocculation - - + -
+ -
+--
negative + -
charge + -
positive Patch - +
flocculation - ++ σ Polymer dosage
charge + +
+ -- i.e.p.
+
- + Polymer dosage
3. Flocculation by - ++
Salt Addition Flocculation

(high charge density

van der Waals (low charge density
low molecular weight Bridging
attraction high molecular weight
polyelectrolytes)
polymers) flocculation
σ Polymer dosage

Al2(SO4)3
Polymer dosage

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Relation between the Polymer Adsorption Effect of pH on the Charge of Polyelectrolytes

and Flocculation Efficiency (cont'd)
cationic quaternary amines
+ + + + + + + + + + 100% + + + + + + + + + +

polyethyleneimine
Residual 100% + + + + 80% + + + 50% + + + 0%
Absorbance

anionic copolymer
- - 0%
- - - - - - - - 50%
- - - - - - - -80%
- - - - - - -100%
--------

i.e.p. Mobility amphoteric copolymer

[μm s-1/V cm-1] ++++++++++++-----------------
PEI
Adsorption
[mg/g] 0 2 4 6 8 10 12
1 [ BH + ]
B + H + R BH + K= =
K base [ B][ H + ] pH1/ 2 = pK acid or base
Addition of PEI [mg/dm3] [ A− ][ H + ]
AH R A− + H + K = K acid =
Flocculation of bleached sulphite pulp due to adsorption of PEI at pH 4.5 and 7.0. [ AH ]

Retention First-pass Retention and True Retention

I. Fibres are retained on the wire forming the paper web.
¾ Retention is a measure of raw material utilization.
II. Fines and additives (fillers, sizing agents, wet strength agents)
¾ First-pass retention relates to the efficiency of the wet end.
are (expected to be) retained by the fibres.
¾ True retention relates to the efficiency of the total papermaking system.
The wire
The fibres 200-mesh screen
do not pass through (75x75 μm holes)
200-mesh screen total solids in headbox - total solids in tray
(L > 100 μm) FPR = x 100%
Fines total solids in headbox
pass through
200-mesh screen
(L ~ 1-10 μm) tonnage conveyed to the press
TR = x 100%
Filler and sizing agent tonnage discharged by the headbox
pass through
200-mesh screen
(L ~ 0.1-10 μm)

Terminology note:
“Consistency” = “Total Solids” in the slurry determined by filtration and drying
N.B. What isn't retained is lost increasing the production cost
and adding to the environmental load.
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4
 The Surface Forces that Control Retention Common Types of Retention Aids

Force type / origin Action range Influenced by Alum(inium sulfate) Polyacrylamides Polyethylene oxide
Hydrolysis (20-70% of cation.subst.)
Headbox hydrodynamics; Al2(SO4)3 → 2Al3+ + 3SO42-
Hydrodynamic
L ~ (ηt/ρ)1/2 Machine speed;
Al3+ + H2O → AlOH2+ + H+
shear Stock viscosity
AlOH2+ + H2O → Al(OH)2+ + H+ 9 Efficiency depends on Mw
Polymer type and Mw; (very high Mw required).
Polymer-induced L ~ 10 nm Al(OH)2+ + H2O → Al(OH)3 + H+
ion strength of the stock 9 High viscosity (handling).
Al(OH)3 + nOH- → Al(OH)3+nn- 9 Non-charged.
Ion strength of the stock 9 Little affected by ionic
Electrostatic
L ~ 0.3 / I 1/2 nm water; pH; type of pulp; composition of stock.
(I - ion strength) amount of ionic additives
Network flocculants
van der Waals L ~ 1 nm -
(SiO2 or Clay)/(PAA or PEO)
Hydration Hydrophobe/hydrophile
L ~ 1 nm
(hydrophobic) balance; surface energy
9 Efficacy depends on Mw
(high Mw is required).
N.B. Role of surface effects is proportional to the surface to bulk ratio, 9 High viscosity.
9 Efficiency depends on pH. 9 Weak chelating properties
Surface π dL 1
∝ ∝ → ∞ as d → 0
Volume π d 2L d Major types of RA's: (i) Inorganic, (ii) Synthetic Polymers, and (iii) Mixed
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Dual Component Coagulant / Flocculant Systems Retention is always affected

by a great number of
difficult-to-predict factors,
e.g.
Usual combinations: coagulation
filler's mineralogy
¾ Alum + PAM
¾ Cationic starch + PAM
¾ PAC + PAM hetero- flocculation
coagulation
¾ Polymine + PAM
¾ PEI + PAM
¾ poly-DADMAC + PAM

and dispersing agent used in filler

Glossary for non-technologists:

PAM = polyacrylamide (cationic or anionic)
PAC = polyaluminium chloride
PEI = polyethyleneimine
DADMAC = di-allyl di-methyl ammonium chloride
… so it's more art than science.
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Examples of Retention Systems

Poly(hydroxy styrene) / polyethylene oxide system for retaining fine particles

(US pat. 5,472,570)
Mw of PHS ~ 1,000 - 2,000
Mw of PEO ~ 4,000,000 - 7,000,000
Weight ratio PHS / PEO ~ 0.5 to 10
Addition level ~ 0.01 to 0.1% by the weight of dry pulp.

Cationic galactomannan / bentonite system for retaining mineral fillers

such as clay, chalk, calcium carbonate, titanium oxide, or bentonite
(US pat. 6,270,626)
Degree of cationic substitution ~ 0.01 to 1%; Mw ~ 2,000,000
Bentonite/galactomannan ratio ~ 1 to 10 by weight
Addition level ~ 0.01 to 5% by the weight of dry pulp.

Note: cationic substitution may be done by reacting hydroxyl groups of the parent polymer
(polyhydroxystyrene, polygalactomannan, starch) with quaternary ammonium compounds.

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