Fiber and Bonds

Introduction
Fibers retain most of their original structure
during pulping and papermaking.
Their properties determine the properties of
paper.

Bonding between fibers is also very important.

Without bonding, there would be no network.

During papermaking, bonding arises from the

intrinsic tendency of cellulosic fibers to bond to
each other when dried from water or other polar
liquid.

 With the obvious importance of fibers and

bonds, it is misleading to view paper as a
collection of inert fibers attached to one
another.
The properties of fibers and bonds in paper
are intimately connected with the network
structure that they form.
The mechanical properties of fibers cut from
a paper sheet differ from the properties of
the same fibers dried individually.

 The connection between the network structure

and the microscopic properties of fibers and
bonds develops during paper drying as internal
stresses generate in fiber networks.
These internal stresses are local and act within
and between fibers.
Macroscopically, the net stress is zero.
The internal stresses depend on the anisotropic
shrinkage potential of the fibers and on the
macroscopic stresses applied during paper
drying.

Fiber Properties
These affect the formation and
consolidation of paper structure during
the papermaking process.
They a responsible for the properties of
dry paper.
Raw materials determine the range of
fiber structures and dimensions that the
pulping process modifies.

 Papermaking pulps consist of

mechanical and chemical pulps that
have different effects on paper
properties.
Paper structure depends on fiber
dimensions and the mechanical
properties of wet fibers.
The mechanical properties of dry fibers
and paper depend on the stresses under
which they were dried.

Raw Materials
Paper consists of wood fibers, but nonwood
fibers can be important in some specialty
papers.
Fiber properties very significantly with wood
species, growth site, pulping and
papermaking treatments.

Because of the stochastic nature of these

variables, the properties of the pulp may
have a wide distribution.

 Figure 1 illustrates the cell wall of a wood fiber.

Often the P and S1 layers are lost in the pulping
process.

The native structure of

the fiber and the
resulting changes to it
during pulping
determine how much
the fiber swells in
water and how
conformable it is.
The final structure of
the fibers depends on the papermaking process.

 If the cell wall is rigid enough, the fiber lumen

may survive uncollapsed.
The S2 layer is usually the thickest and
dominates mechanical properties.
In the S2 layer micro fibrils spiral around the
fiber axis at a constant fibril angle.
The fibrils are small bundles of primarily
cellulose molecules.
The values of the fibril angles vary, even within
a given wood species, but the the chirality of the
spiral is always right handed.

 The S1 and S3 layers also have a spiral fibril

structure, but they contribute much less to
mechanical properties than S2.

In the cell wall, a matrix of amorphous

hemicellulose and lignin surround the fibrils.
This matrix is ductile compared to the stiff fibrils.
The fibrils give the fiber its elastic modulus and
tensile strength in the axial direction.

Strength improves as the fibril angle decreases.

Fibers are plant cells that have a high aspect
ratio, as shown in Table 1 on the next slide.

 The pulp plants have other cells that may

strongly influence the pulp quality.
For some trees, such as beech, only 40% of the
volume is fibers.
These nonfiber cells, such as parenchyma cells
and vessel elements can have harmful effects
on pulping and bleaching processes.
They also effect the linting and printability of
paper.
The absolute length of fibers is one of the most
important characteristics of papermaking fibers.

 A long fiber can have can have more bonds

with other fibers and therefore will be held
more strongly than a short fiber.

The tensile strength of the wet web increases

rapidly with fiber length.
Likewise, tensile strength, breaking strain and
fracture toughness also increase with fiber
length.
Hardwood fibers are shorter than softwood
fibers.

 Figure 2 shows that hardwood fibers also have

a narrower length distribution.
It is common to
express the average
fiber length as the
length weighted
average length.
This choice is
motivated by
geometric arguments.
The probability of two fibers crossing is
proportional to the the mean value of fiber
length squared.

 The fiber length times the perimeter of the

cross-section defines the outer surface area of a
fiber.

This outer layer can form inter-fiber bonds or

scatter light when not bonded.
The cell wall thickness, df, and fiber perimeter,
Pf, determine the cross-sectional area of dry cell
wall, Af.

For circular cross-sections we have the

following relationship;
Af=(Pf-pdf)df

 This also holds for fibers with noncircular crosssection, providing the cell wall cross-sectional
area doesn't change after collapse.

Fiber coarseness wf, gives the dry fiber mass

per unit length.
It is equal to the cross-sectional area times the
density of the cell wall.
Coarseness tends to
correlate with fiber
length in the sense
that long fibers are
coarser than short fibers, as shown in Figure 3.

 Fiber coarseness divided by the fiber width

gives the basis weight, bf, of fibers.
Basis weight of fibers varies from 3-10 g/m2.

For shortwood fibers, the basis weight and

coarseness are often related as suggested by
Table 2 below.
Note that fiber dimensions are usually
measured in the wet state.

 This has little significance for fiber length, but

the cross-sectional dimensions of dry fibers are
smaller than those of wet fibers.

The basis weight of fibers in paper are generally

larger than those in Table 2, which are based on
wet fibers.
The basis weight of fibers is important, because
the coverage of paper is equal to b/bf, as we
saw in Chapter 1.
Likewise the total length of fibers in a sheet of
area A is given by
L=bA/wf

 Thus, a cm2 of a paper sheet has a total fiber

length of 10-100 m, corresponding to 10,000100,000 fibers.

In areas where summer and winter seasons are

clearly identifiable, softwoods and some hard
woods show a seasonal variation in growth.
This is reflected in variation in wood density and
fiber dimensions.
Early in the growing season, thin walled fibers,
springwood or earlywood, grow with large
lumen.

 The fiber dimensions later change gradually,

with the fiber wall becoming thicker and the
lumen becoming smaller.

Fiber perimeter may even decrease.

Thick-walled fibers form the summerwood or
latewood portion of the growth ring.
The variation in coarseness between
springwood and summer wood can be greater
the the differences in average coarseness for
different softwoods.
Not the entry for Scots (Scotch) pine in Table 2.

Pulping effects
After the effects of raw materials, the effects of
pulping, bleaching and beating are crucial.
As we know, the two important classes of pulp
are chemical pulp (usually bleached kraft) and
mechanical pulp.
The differences in fibers for these pulps are
illustrated in Figure 4 below.
For chemical pulp,
wood is disintegrated
into fibers chemically
by cooking wood chips.

 For mechanical pulp the process is a

mechanical one as with TMP or GW.
Some wood species, such as Norway spruce,
aspen and radiata pine can be used
successfully for both chemical and mechanical
pulp.

Others such as Scotch pine, eucalyptus and

birch are work better for chemical pulping.
Chemical and mechanical pulping give distinctly
different sheet properties.
Paper from bleached kraft pulp has 2-3 times
the tensile strength that from mechanical pulp.

 On the other hand, the opacity and light

scattering power form mechanical pulps are
superior to those from kraft pulp.

This results from the contribution of fines in

mechanical pulp.
The differences between chemical and
mechanical pulps are utilized in many paper and
board grades.
Newsprint often consists of purely mechanical
pulp, while copy paper consists of purely
chemical pulp.

 Mixtures of mechanical and chemical pulps are

used in printing papers and multi-ply boards.
The differences between chemical and
mechanical pulps are illustrated in Table 3.
The lignin content in mechanical pulps is
approximately 30 %
and essentially zero
for bleached kraft pulps.
The low lignin content
gives kraft fibers higher
wet fiber flexibility,
collapsibility and
swelling ability.

 However, since the lignin and hemicelluloses

are removed, chemical pulps give lower raw
pulping yields as a percentage of wood mass.

As a result, the mechanical pulping process

generates fiber fragments and other small
particles called fines.
In chemical pulps, fines include ray cells and
parenchyma cells in addition to particles coming
form fiber walls.
20-40% of mechanical pulp and less than 10%
of chemical pulp is considered as fines.

 The fraction of long, intact fibers may be less

than 20% in GW pulp, nearly 40% in TMP
pulp and as high as 90% for chemical pulp.
The weight per unit length of chemical pulp
fibers is half that of mechanical pulps
because of the difference in yields.

For example a 20-80% mixture of kraft pulp

and ground wood, respectively has
approximately equal numbers of chemical
and mechanical long fibers.

 Mechanical pulping produces pulp that can be

used directly, but it often undergoes bleaching.
Chemical pulp is also bleached most of the
time.
The principal use of unbleached pulp is in
packaging boards and papers.
Even for packaging, the public is demanding a
more attractive printable surface.
The bleaching process enhances brightness, of
course, but also alters the mechanical
properties of wet and dry fibers.

 The bonding ability of fibers may improve, but

the tensile strength may deteriorate in
bleaching.
Chemical pulp is beaten to optimize the
contribution to mechanical properties of paper.

The beating of chemical pulp loosens the

structure of the fiber wall (internal fibrillation).
It also may break fragments from the fiber
wall.
Mechanical pulp produces similar effects.

 Internal fibrillation involves partial delamination

of the fiber wall as shown in Figure 5.
The delamination increases the degree of
swelling, the flexibility and conformity of the
wet fiber wall.

This improves
the inter fiber
bonding and
strength at the
expense of
optical properties.

 External fibrillation, where fibrils spread out from

the fiber surface, is apparent from Figure 6.
External fibrillation enhances sheet
consolidation and enforces bonding.

 The external fibrillation occurs only in aqueous

suspension.
Removal of water on drying brings the external
fibrils back to the fiber surface.
The pores close between the lamella and fibrils
in the fibril wall.
Once dried pulp swells less on rewetting than
before drying.
This irreversible loss of swelling ability, called
hornification, is one way recycled fibers differ
form virgin fibers.

 Recycled fibers are generally shorter, stiffer,

more curly and more brittle than virgin fibers.
Dewatering tests can assess fines content and
the degree of external fibrillation.
These tests measure how easily water drains
from the papermaking pulp.
The Schopper-Riegler number (SR) or
Canadian Standard Freeness (CSF) are the
most common dewatering tests.
The SR number increases with beating and
fines content while the CSF decreases.

Fines
The properties of fines differ greatly from the
fiber fractions.
The common definition of fines is the fraction
that passes through a 200 mesh screen.
The median size of fines is a few microns.
The largest fines particles are fiber fragments
and the smallest are fibrils, whose size can be
below 1 micron.

 Fines consist of cellulose, hemicellulose, lignin

and extractives.
In chemical pulp the hemicellulose content of
fines is higher than in the fiber fraction.
For mechanical pulps the lignin content of fines
is higher than in the fiber fractions.
Because of their small size and large surface
area, fines can bind more water and swell more.
Hydrophobic lignin fines and extractives in
mechanical pulps reduce their ability to swell in
water relative to fines in chemical pulps.

 The fines content strongly influences the

structure and properties of the fiber network for
mechanical pulps.

A fine stone GW pulp for magazines can have

up to 50% fines, while a newsprint TMP typically
are less than 25% fines.
The fines content in mechanical pulps grow in
the order TMP>PGW>SGW when compared at
the same freeness.
The amount of fines is lower in chemical pulps
than in mechanical pulps.

 There are two types of chemical pulp fines,

primary and secondary fines.
Primary fines are present in unbeaten pulps.
They consist of parenchyma cells from the
wood.

Beating creates secondary fines.

These include lamellar and fibrillar parts of the
fiber wall and some colloidal material.
The primary fines content of chemical pulps is
usually less than 2%, but beating can increase it
to 15%.

 Mechanical pulp fines are sometimes also

divided into primary and secondary fines.
The primary fines result from the mechanical
disintegration of wood.
Secondary fines result from refining of fibers.
The two fractions of a GW pulp are Mehistoff
(Powders) and Schleimstoff (well-bonding
fibrillar particles)
Fines have a very large specific surface area,
because of their small size.
Refining and beating increase the surface area
further.

 In chemical pulps, the specific surface area of

primary fines is 4-5 m2/g, while that of
secondary fines is 10-20 m2/g.

Mechanical pulp finer have 7-8 m2/g, while

fibers have a value of about 1 m2/g.
Because of their large surface area, fines
improve bonding between fibers.
Most fines are bonded to fibers when the paper
dries.
Chemical pulps bond almost completely, while
mechanical pulp fines retain some free area.

Wet Fiber Properties

The network structure depends on
collapsibility, conformability and flexibility of the
wet fibers,
Conformable fibers bend and match the shape
of each other to give a dense and well bonded
network.
Conformability of fibers depends on their crosssectional dimensions, internal fibrillation,
chemical composition and morphology of the
cell wall.

 Fibers have a circular or rectangular crosssection in wood that may flatten or collapse to a
ribbon in the pulping and papermaking process.

The perimeter doesn't change with fiber

collapse.
Fiber collapse is more common with chemical
pulp fibers than with mechanical pulp
fibers.Springwood fibers collapse more easily
than summerwood and sulfite fibers collapse
more easily than kraft fibers as shown in Figure
7 on the next slide.

 For uncollapsed fibers, the lumen scatters light.

Fiber collapse has a
negative effect on the
optical properties of
paper.
Collapsed ribbon-like
fibers are flexible and
can have a higher
bonded area than
uncollapsed fibers.
Fiber collapse does
improve strength.

 Wet fiber flexibility (WFF) or its inverse wet fiber

stiffness is sensitive to
conformability.
WFF measurements
are usually limited to
long fibers.

WFF decreases rapidly

with increasing fiber
thickness as shown in
Figure 8.
Thick beams have a
higher bending
stiffness than thin.

 As shown in Figure 9, WFF increases with

decreasing yield and increased beating.
Mechanical pulp fibers usually have a lower
WFF than chemical pulp fibers.
The effect of beating
and yield on fiber
flexibility probably
results from an
increase in the
porosity or
delamination of the
cell wall.

 Swelling degree of fibers depends on chemical

composition and internal fibrillation.
Hemicellulose promotes fiber swelling and lignin
inhibits it.
Chemical pulps swell more than mechanical
pulps.

The swelling of chemical pulp fibers increases

with beating.
The swelling is characterized by the WRV, or
water retention value.
Its measurement gives the amount of water
contained by the pulp after centrifugation.

Mechanical Properties of Dry Fibers

Figure 10 shows the wide distribution of tensile
strength values.
This variability results from biological raw
material and from the nonuniformity of pulping
processes.
Even selection of
fibers can cause
biases, because one
tends to pick long
straight fibers for
testing.

 Due to the poor statistics of single fiber

measurements, the zero span strength is often
taken as a measure of fiber strength.

Care must be exercised when doing this

because the results
can depend on other
factors.
The load-elongation
effect of single fibers
is qualitatively similar
to paper when the fibril
angle is small as
shown in Figure 11.

 The elastic modulus of the fiber in the axial

direction is obtained from the initial linear
section of the load elongation curve.

The nonlinearity in the load-elongation curves

arises from curl and defects, such as crimps,
kinks and microcompressions.
Fibers with no defects are nearly linearly
elastic (Hookian).
The cell wall of a fiber can have a large number
of dislocations and other inhomogeneities that
reduce the elastic modulus, tensile strength and
breaking strain.

 Natural defects, such as pits may also exist.

Defects arise from during chipping, pulping and
refining.

Typical tensile strength values of wood fibers

are 100-200 mN as shown in Table 4 for spring
and summer wood fibers.
Breaking stress values of other natural cellulosic
fibers are similar to wood fibers.

These are 300-800

MPa for cotton and
200-300 MPa for
viscose.

 Table 4 shows that the force necessary to

break a summerwood fiber is higher than that
to break a springwood fiber.
This results form summerwood's higher
cross-sectional area.
They have a higher breaking stress than
springwood fibers.
The thicker S2 layer and smaller fibril angle in
summerwood fibers contribute to their higher
tensile strength.

Fibers of high fibril angle have a higher breaking

strain and lower tensile strength than those of
lower fibril angle as shown in Figure 11.
Figure 12 shows that the elastic modulus of fibers
also increases with decreasing fibril angle.
In pulping, gentle
removal of lignin does
not change the force
required to break a fiber.

This implies that lignin

and hemicellulose give
no contribution to
tensile strength

Effects of Drying Stress

Jentzen effect:
Jentzen showed that
drying under an axial
tension increases
tensile strength and
decreases breaking
strain.
This is shown in
Figure 13.
The opposite occurs
when fibers are dried under axial compression.

This is shown in Figure 14.

The mechanism of these effects are illustrated

in Figure 15.

With this mechanism, the drying tension;

1. reduces fibril angles,
2. aligns molecules parallel to the external
load,
3. straightens the fiber, and

4. pulls out dislocations and other defects.

High hemicellulose content is beneficial for the

Jentzen effect.

The swollen state of the hemicellulose matrix

is necessary for the structure and molecular
rearrangement of fiber during drying.

 If dried and rewetted, kraft fibers dried

under load show no Jentzen effect.
Drying causes irreversible changes in the
fiber wall structure.

The Jentzen effect shows how much drying

conditions can change fiber properties.
It demonstrates the importance of internal
stresses generated during the drying
process.

Bonding
Inter-fiber bonds were studied extensively
during the 1950s and 60s.
These studies still retain fundamental value.
In this section we will explain the chemical
effects of bonding between wood fibers.
We will explain the formation of inter-fiber
bonds.
Finally, we sill discuss the strength of these
bonds.

Basic Concepts

There are various types of interactions

involving fibers that are sometimes referred to
as bonds.

These are;

1. Normal chemical bonds within cellulose

molecules.
2. Intermolecular Van der Waals bonds, much
weaker than chemical bonds.

3. Entanglements of polymer chains.

4. Inter-fiber bonds: fibers are so close that any
of the above may occur.

Molecular Bonding
Hydrogen bond a special type of almost
chemical bond.
A covalent bond is
typically~150-500
KJ/mol.

For hydrogen bonds,

the energy is typically
~8-32 kJ/mol, e.g.
O-H6O3 and
O2-HO6 , the OH
distance ~ 0.17 nm
versus O-H~0.1nm.

 Besides hydrogen bonds, van der Waals forces

are important for inter-fiber bonding.
The van der Waals force is typically~2-8
KJ/mol.
This interaction is relatively long range,
extending to distances of 0.3-0.5 nm.
Much of the cohesion of wet paper comes form
van der Waals bonds.
In addition covalent and ionic bonds may form
between fibers and polymeric mediators.

Structure of Inter-fiber Bonds

Inter fiber bonds in paper form gradually as
solids content increases.
First, surface tension forces, such as colloidal
interactions, and interlocking of fibrils pulls
fibers closer together as water is removed
from the wet web.

This is called the Campbell effect.

These same forces give the wet paper web its
tensile strength.

 Fines improve sheet consolidation and bond

formation because of their large specific surface
area.

The Campbell forces increase with the surface

area of the pulp.
Fiber-water interactions influence inter-fiber
bond formation.
Water between two cellulosic chains forms
hydrogen bonded chains.
As water is removed, the chains become shorter
and hydrogen bonds form between cellulose
molecules.

 Fibers shrink during drying.

The amount of depends on the swelling degree
of the fiber wall.

Shrinkage in lateral direction and stiffness in

longitudinal direction generate shear stresses as
shown in Figure 17.
Shear stresses at
inter-fiber bonds
generate axial
compressive forces,
called
microcompressions on
the crossing fibers.

Nanko and Ohsawa studied the structure of

fiber bonds of a bleached kraft pulp, using a
transmission electron microscope.

Figure 18 summarizes these findings.

They identified four main features;

1. Bonding layer,
2. wrinkles,
3. skirt, and
4. covering layer.

Bonding Strength
The strength of inter-fiber bonds usually refers
to shear strength.

Sometimes the bond strength is characterized in

terms of the out of plane delaminating energy.
This is generally measured in a peeling test
Another important issue is the area of a bond.
The specific bond strength is defined as the
ratio of bond strength and area.
Button modeled the bond between fibers as a
lap joint as shown in Figure 19 on the next slide.

 The stress distribution within a bond is

nonuniform when loaded in shear.
The highest stresses occur at the edges of the
bond.
Button concluded that
bond strength, or
breaking load, is
almost independent of
bond length or area,
but increases as the
square root of
thickness or axial
strain modulus.

Fibers and Bonds in Paper

Deformations in the internal structure of fibers
and bonds explain qualitatively the microscopic
and macroscopic changes that occur during
drying
These are usually explained in terms of internal
stresses, dried-in stresses or dried-in strains.
The dried-in stresses are different in MD and
CD directions because of the anisotropy of the
process.
The effects of web tension and stretching in the
MD are very important.

Internal Stresses
During drying, the external macroscopic
stresses are distributed in the fiber network
largely based on local structure.
Wood fibers shrink in the transversal
direction primarily, with little change in the
longitudinal direction.

This transverse shrinkage causes

compressive stresses in the axial direction
of surrounding fibers.

 The compressive stresses act on each fiber as

illustrated in Figure 20.
For a uniaxially restrained sheet, the axial
shrinkage of fibers is ten times smaller than the
transverse shrinkage.

In the lateral direction

of the sheet, where
macroscopic shrinkage
is unconstrained, the
difference is less, but
still significant.

 The drying shrinkage of a fiber is an average

over bonded and free segments.
For a bonded segment, the balance of the
following three forces determines the axial
compression:
Compressive force by the transverse
shrinkage of crossing fiber,
Tension or compression arising from the
drying stress,
Reaction force governed by the axial stiffness
of the bonded segment.

 The compressive force is larger than the

macroscopic drying stress and bonded fiber
segments generally shrink during drying as
illustrated in Figure 21.
For free fiber
segments, the
compressive force
arises from the
shrinkage of
neighboring bonded
segments.

 Thus, the force is smaller than that on bonded

segments, because it transmits through the
surrounding network.
Thus, free segments
compress less than
bonded segments.

Refining increases
shrinkage, because it
increases the swelling of
wet fibers.
The resulting
distribution of shrinkage for fiber segments is
given in Figure 22.

 Different drying stresses on free and bonded

segments affect the three-dimensional structure.
If sheet shrinkage is allowed, consolidation may
lead to bonds where flexible fibers partially wrap
around crossing fibers as illustrated in Figure
23.
Bonded segments
under compression
have a lower axial
modulus than free
segments due to the
Jentzen effect.

Macroscopic Drying Shrinkage

The product of the shrinkage potential and
the elastic modulus gives the compressive
stresses due to drying that are balanced by
external applying stresses applied to the
web.
If the drying rate is low
or drying temperature
is high, the drying
stress is low as
illustrated in Figure 24.

 The applied stresses before approximately 60%

of solid content have the largest effects on the
elastic modulus.

The drying shrinkage at the edges is larger than

at the center of the web.
Figure 25 shows examples of the shrinkage
profile on paper machines.

 The CD drying shrinkage and the amplitude of

its variation increases with refining.
CD elastic modulus and tensile are lower at the
edges than in the center.
The CD breaking strain and hygroexpansivity in
CD are larger than in the MD.
The basis weight is larger at the edges than in
the center.

Reducing the opening of the slice in edge

portion reduces the basis weight variation, but
may lead to an orientation of fibers as was
discussed previously.

Wet Straining in Paper Web

Stretching in MD causes a contraction in CD as
shown in Figure 26.

Woodfree furnishes have a smaller Poison ratio

than wood-containing furnishes.

Effect on Network Structure

Stretching tends to amplify the effects of poor
formation paper.
This results in a decrease in the strength of
the wet web.
The average basis weight of the paper
decreases in proportion to wet strain.

In the thickness direction, wet pressing has

caused z-directional bends or undulations in
fibers that can now be pulled straight.

 This is illustrated in Figure 27.

This mechanism also
applies to fibers that
are aligned close to
the machine direction.
However, the shape of
CD fibers may change
as well.
As fibers are
straightened,
thickness increases,
RBA decreases, modulus increases in MD but
decreases in CD.