polymers

Article
Pulp Fines—Characterization, Sheet Formation,
and Comparison to Microfibrillated Cellulose
Wolfgang Johann Fischer 1,2 , Melanie Mayr 1 , Stefan Spirk 1 , David Reishofer 1 ,
Lukas Andreas Jagiello 1,3 , Romana Schmiedt 1 , Jerome Colson 4 , Armin Zankel 5
and Wolfgang Bauer 1, * ID
1 Institute of Paper, Pulp and Fibre Technology, Graz University of Technology, Inffeldgasse 23,
8010 Graz, Austria; WolfgangJohann.Fischer@sappi.com (W.J.F.); melanie.mayr@tugraz.at (M.M.);
stefan.spirk@tugraz.at (S.S.); david.reishofer@tugraz.at (D.R.); l.jagiello@zellstoff-poels.at (L.A.J.);
office.ipz@tugraz.at (R.S.)
2 Sappi Paper GmbH, Brucker Str. 21, 8101 Gratkorn, Austria
3 Zellstoff Pöls AG, Doktor-Luigi-Angeli-Straße 9, 8761 Pöls, Austria
4 Department of Materials Sciences and Process Engineering, Institute of Wood Technology and Renewable
Materials, University of Natural Resources and Life Sciences Vienna, Konrad-Lorenz-Straße 24,
3430 Tulln, Austria; jerome.colson@boku.ac.at
5 Institute for Electron Microscopy and Nanoanalysis, NAWI Graz, Graz University of Technology and Centre
for Electron Microscopy, 8010 Graz, Austria; armin.zankel@felmi-zfe.at
* Correspondence: wolfgang.bauer@tugraz.at; Tel.: +43-316-873-30750

Received: 28 July 2017; Accepted: 13 August 2017; Published: 17 August 2017

Abstract: In the pulp and paper industry different types of pulp or fiber fines are generated
during the pulping (primary fines, mechanical fines), and/or the refining process (secondary fines).
Besides fibers, these cellulosic microparticles are a further component of the paper network. Fines,
which are defined as the fraction of pulp that is able to pass through a mesh screen or a perforated
plate having a hole diameter of 76 µm, are known to influence the properties of the final paper product.
To better understand the effect and properties of this material, fines have to be separated from the
pulp and investigated as an independent material. In the present study, fines are isolated from the
pulp fraction by means of a laboratory pressure screen. To allow for further processing, the solids
content of the produced fines suspension was increased using dissolved air flotation. Morphological
properties of different types of fines and other cellulosic microparticles, such as microfibrillated
celluloses (MFC) are determined and compared to each other. Furthermore, handsheets are prepared
from these materials and properties, such as apparent density, contact angle, modulus of elasticity,
and strain are measured giving similar results for the analyzed types of fines in comparison to the
tested MFC grades. The analysis of the properties of fiber fines contributes on the one hand to a better
understanding of how these materials influences the final paper products, and on the other hand,
helps in identifying other potential applications of this material.

Keywords: pulp fines; fiber fines; microfibrillated cellulose; sheet forming; vacuum filtration;
tensile properties; contact angle; surface roughness

1. Introduction
Paper is a non-woven fibrous cellulose based material, which is formed by an interaction of
individual fibers to form a network with a complex hierarchy and porosity. The large fraction of
this network consists of pulp fibers, which have been subjected to a variety of treatments depending
on the envisaged application for the final paper products. During these treatments in pulping and
papermaking processes, cellulosic microparticles are formed, the so-called fines. Fines are defined

Polymers 2017, 9, 366; doi:10.3390/polym9080366 www.mdpi.com/journal/polymers

Polymers 2017, 9, 366 2 of 12

as the fine cellulosic particles, which are able to pass through a 200 mesh screen (equivalent hole
diameter 76 µm) of a conventional laboratory fractionation device (SCAN-CM 66:05). There are
two major types of fiber fines, namely primary and secondary fines. Primary fines are generated
during pulping and bleaching, where they are removed from the cell wall matrix by harsh chemical
and mechanical treatment. As a consequence of their origin (i.e., compound middle lamella, ray cells,
parenchyma cells), primary fines exhibit a flake-like structure with only minor shares of fibrillar
material [1,2]. In contrast, secondary fines are generated during the refining of pulp. In this case,
a mechanical treatment partially induces fibrillation of cell wall fractions, resulting in the formation
of a fibrillated material that has microscopic dimensions [3,4]. Both types of fines are usually present
in a papermaking furnish. However, due to their differences in morphology and chemistry, which is
also dependent on the type of the pulping process, they have a different impact on paper quality
and product performance [2,5,6]. Particularly the large aspect ratio, surface area, and bonding ability
of secondary fines enhance the mechanical strength of papers, while having a negative influence
on dewatering in the forming section of a paper machine. Primary fines mainly affect the optical
properties of the final papers [2,7,8], but also have a negative effect on dewatering, and in some cases
also on mechanical paper properties. Because of their large specific surface area in comparison to pulp
fibers, fines also consume a high proportion of chemical additives used in pulp and paper production.
Fines usually are an inevitable, but undefined part of papermaking furnishes. Although in
principle their effects on paper properties, being it sheet densification, strength improvement,
deterioration of dewatering, etc. are known, their impact is often difficult to quantify. The partly
negative effects of fines on process performance and paper properties are also a motivation to consider
the removal of fines from papermaking furnishes.
There are two major issues when it comes to the fines fraction in papers. The first is related to
the analysis of the distribution of the types of fines in papermaking furnishes and in paper, which is
not a straightforward task [9]. The second is related to the isolation of the fines from paper pulps,
which involves laborious separation steps (e.g., screening, centrifugation, etc.), resulting in suspensions
with dry weight contents of 0.1 wt % and below [10–14]. Consequently, the removal of water to obtain
higher dry weight contents is a major challenge. In contrast to microfibrillated celluloses (MFCs),
which recently entered into the market, pulp fines so far are not commercially available. This is certainly
associated with the above-mentioned problems in analysis and production/separation, as well as
a lack of detailed investigations on their properties.
In the production of MFCs, various kinds of mechanical treatments are applied, such as high
pressure homogenization, microfluidization, grinding, cryo-crushing, steamexplosion, and high
intensity ultrasonfication, as summarized in a review by Osong et al. [15]. All these techniques
require a significantly higher energy input of up to 30,000 kWh/t when compared to conventional
refining [15]. Depending on the applied technique a more or less homogeneous MFC material is
produced. In a microfluidizer, for example, the material has to undergo several homogenization
passes to achieve a homogeneous fibrillation. Fibrillation is improved by chemical or enzymatical
pretreatment to reduce energy consumption [16], but pretreatment and multiple passes are a cost
factor in MFC production. In conventional refining, fibrillar (secondary) fines are produced at much
lower energy levels than in MFC production. These fines, however, have to be separated from the
remaining fibers in order to use it as a MFC substitute. Microfribrillation is directly related to the
gap-clearance of the refiners, which is rather high in conventional refining when compared to super
grinders, and thus tends to produce a coarser material. MFC is defined to have a length between 0.5 to
100 µm, and a width from 10 to 100 nm [15]. Since fines are defined as the particles passing through
a 200 mesh screen, they contain also larger particles. For example, primary fines having a flake-like
structure show dimensions of up to 350 µm × 25 µm in the fines fraction [17].
In this paper, we attempt to address the challenge of fines separation by first introducing an elegant
method to upscale the production/separation method for fines to kg scale, then we investigate the
Polymers 2017, 9, 366 3 of 12

sheet formation
Polymers 2017, 9, 366using
different types of fines, and finally compare their performance to commercially 3 of 12
available MFC products.
2. Materials and Methods
2. Materials and Methods
All tests have been performed using primary and secondary fines, separated from never-dried,
All testssoftwood
unbleached have been performed
kraft pulp (a using primary
mixture andand
of spruce secondary fines, separated
pine), never-dried, from never-dried,
bleached sulfite pulp
unbleached softwood kraft pulp (a mixture of spruce and pine), never-dried,
(spruce), as well as mechanical pulp fines from never-dried, bleached pressure ground bleached sulfitewood
pulp
(spruce), as
(spruce). well as mechanical
Furthermore, pulp fines from
two commercially never-dried,
available bleached pressure
microfibrillated ground
cellulose woodand
samples, (spruce).
one
Furthermore, two commercially available microfibrillated cellulose samples, and one
experimental MFC grade from an institution, that does not want to be disclosed, were used. The experimental
MFC grade
analyzed from an
samples institution,
are summarized thatindoes not1.want to be disclosed, were used. The analyzed samples
Table
are summarized in Table 1.
Table 1. Fines and microfibrillated celluloses (MFC) samples used in this study.
Table 1. Fines and microfibrillated celluloses (MFC) samples used in this study.
Type of Fines/MFC Labelling of Samples
Type of Fines/MFC
Never-dried, bleached sulfite pulp, primary fines Labelling of Samples
B PF sulfite pulp
Never-dried, bleached sulfite pulp, secondary
Never-dried, bleached sulfite pulp, primary fines fines B SF sulfite pulp
B PF sulfite pulp
Never-dried,
Never-dried, bleached
unbleached sulfite pulp,
softwood secondary
kraft fines fines
pulp, primary BUB
SF sulfite pulp
PF kraft pulp
Never-dried, unbleached softwood kraft pulp, primary
Never-dried, unbleached softwood kraft pulp, secondary fines fines UB PF kraft
UB SF kraft pulp
pulp
Never-dried, unbleached softwood kraft pulp, secondary fines UB SF kraft pulp
Bleached
Bleachedpressurized
pressurized ground wood(PGW),
ground wood (PGW), fines
fines MPMP fines
fines
MFCMFC1 1(experimental MFC,undisclosed
(experimental MFC, undisclosed source)
source) MFC
MFC 1 1
MFC
MFC2 2(commercially availableMFC
(commercially available MFC A)A) MFC
MFC 2 2
MFC3 3(commercially
MFC (commercially available
availableMFC
MFC B) B) MFC
MFC 3 3

2.1. Separation and Thickening of Fines

In order to separate the fines from the pulp, a purpose-built laboratory pressure screen was
employed. This
This newly
newlydesigned
designeddevice
deviceisiscapable
capableof of
separating
separatingfines from
fines pulps
from in kilogram
pulps scalescale
in kilogram [10].
Figure
[10]. 1 depicts
Figure the pressure
1 depicts screen
the pressure used used
screen in theinpresent study.study.
the present

Figure
Figure 1.
1. Pressure
Pressure screen
screen for
for separating
separating fines
fines from pulp.
from pulp.

In the first step of fines separation, the pulp was diluted with water to a consistency of 0.5 to 1
In the first step of fines separation, the pulp was diluted with water to a consistency of 0.5 to
wt %, and stirred for about 10 min. This suspension was pumped through the pressure screen (PS),
1 wt %, and stirred for about 10 min. This suspension was pumped through the pressure screen (PS),
whose main element is a perforated strainer with hole diameters of 100 μm. Larger particles will not
whose main element is a perforated strainer with hole diameters of 100 µm. Larger particles will not
pass the strainer, and are transferred back to the feed tank. The fines fraction that is able to pass the
pass the strainer, and are transferred back to the feed tank. The fines fraction that is able to pass the
strainer is collected in a separate barrel. Due to the low solid content of the fines suspension (0.02%,)
a subsequent thickening step is needed. For this task, a laboratory flotation cell, which can be directly
connected to the PS, is implemented. The flotation cell developed at the Institute of Paper, Pulp and
Fibre Technology (Graz, Austria) is shown in Figure 2.
Polymers 2017, 9, 366 4 of 12

strainer is collected in a separate barrel. Due to the low solid content of the fines suspension (0.02%,)
a subsequent thickening step is needed. For this task, a laboratory flotation cell, which can be directly
connected to the PS, is implemented. The flotation cell developed at the Institute of Paper, Pulp and
Fibre Technology
Polymers 2017, 9, 366(Graz, Austria) is shown in Figure 2. 4 of 12

Figure2.2.Flotation
Figure Flotationcell
cellfor
forthickening
thickeningofoffines
fines(left);
(left);magnification
magnificationofof the
the airair injection
injection system.
system.

The fines suspension is pumped from the feed barrel to the flotation cell. Air is injected into the
The fines suspension is pumped from the feed barrel to the flotation cell. Air is injected into
suspension with a needle positioned directly before the pump (see Figure 2, magnification right). The
the suspension with a needle positioned directly before the pump (see Figure 2, magnification right).
air flow can be adjusted by an air control valve. Shear forces inside the pump lead to the collapse of
The air flow can be adjusted by an air control valve. Shear forces inside the pump lead to the collapse of
the air bubbles, and finally to the dissolution of air. Due to a pressure drop, controlled with a pressure
the air bubbles, and finally to the dissolution of air. Due to a pressure drop, controlled with a pressure
relief valve, the air is released in the form of fine bubbles (Ø ~ 60 μm). The fines, attached to the air
relief valve, the air is released in the form of fine bubbles (Ø ~ 60 µm). The fines, attached to the air
bubbles, rise to the surface of the water layer in the flotation cell and can be collected in the collection
bubbles, rise to the surface of the water layer in the flotation cell and can be collected in the collection
pan. Using this method, the solid content can be increased by up to 4% [10]. In contrast to other
pan. Using this method, the solid content can be increased by up to 4% [10]. In contrast to other
flotation methods, a major advantage here is to avoid the use of any chemicals in the course of the
flotation methods, a major advantage here is to avoid the use of any chemicals in the course of the
applied flotation process.
applied flotation process.

2.2.Lignin
2.2. LigninContent
Contentand
andMorphological
MorphologicalProperties
PropertiesofofFines
Finesand
andMFC
MFC
Foreach
For each ofof the
the materials,
materials, thethe κ-number,
κ-number, as an
as an indication
indication for for
the the lignin
lignin content
content of a of a certain
certain pulppulp
or
or pulp fraction, was determined according to ISO 302:2015. An approximation
pulp fraction, was determined according to ISO 302:2015. An approximation of the mass fraction of the mass fraction
of
of lignin can be obtained by multiplying the κ-number
lignin can be obtained by multiplying the κ-number by 0.15 [18]. by 0.15 [18].
Themorphological
The morphologicalproperties
propertiesofofthe thefines,
fines,asaswellwellasasofofthethemicrofibrillated
microfibrillatedcellulose
celluloseareare
determined using the L & W Fiber Tester Plus (ABB, Mannheim, Germany).
determined using the L & W Fiber Tester Plus (ABB, Mannheim, Germany). Morphological features of Morphological features
of even
even small cellulosic
small cellulosic microparticles
microparticles can be(resolution:
can be detected detected 3.3 (resolution:
µm/pixel).3.3Theμm/pixel). The size
size measurement
measurement was carried out on the fines fraction obtained using the pressure
was carried out on the fines fraction obtained using the pressure screen, MFC samples were measured screen, MFC samples
were measured
without without
fractionation. No fractionation.
size definitionNo size definition
criteria criteria of
of the instrument the applied.
were instrumentForwere
eachapplied. For
test, a dry
each test, a dry sample (0.1 g) is diluted with 150 mL of deionized water.
sample (0.1 g) is diluted with 150 mL of deionized water. A minimum of 100.000 particles was detected. A minimum of 100.000
particles
For was detected.
each sample, For each
two replicates havesample, two replicates
been performed. have been
The results performed.
of these The results
measurements of these
are expressed
asmeasurements
the average circle are equivalent
expressed as the average
diameter (CEDcircle equivalent diameter (CEDq2, Equation (1)), which
q2 , Equation (1)), which in terms of irregularly formed
particles, can be used instead of the length weightedinstead
in terms of irregularly formed particles, can be used averageofparticle
the length weighted
length average
[4]. The CED particle
is the
length [4]. The CED is the diameter of a circle CED i of equivalent area than the projection area Ai of
diameter of a circle CEDi of equivalent area than the projection area Ai of the particle (Equation (2)).
theanparticle
For (Equation
illustration of the(2)). For an between
differences illustrationtheseof the differences
samples between
additional these
images samples
using additional
a conventional
images using a conventional transmission light microscope (Leica
transmission light microscope (Leica 301–371.010) were captured. Details regarding this method 301–371.010) were captured.
are
Details regarding
described in [4]. this method are described in [4].

CEDi3 (1)
CED q2 = (1)
CEDi2
4
(2)
Π

2.3. Fines and MFC Sheet Formation

In order to prepare handsheets from pure fines and MFC, a vacuum filtration method is used. A
 Polymers 2017, 9, 366 5 of 12

r
4 × Ai
CEDi = (2)
Π

2.3. Fines and MFC Sheet Formation

In order to prepare handsheets from pure fines and MFC, a vacuum filtration method is used.
Polymers 2017, 9, 366 5 of 12
A defined amount of fines or MFC (0.24 g, dry weight) is diluted with deionized water to reach a solid
contentofof0.2
content 0.2wtwt%.%. This
This suspension
suspension is stirred
is stirred at 450
at 450 rpm rpm
for for at least
at least 2 h.2After
h. After stirring,
stirring, the sheets
the sheets are
are formed by vacuum filtration using a Britt Dynamic Drainage Jar (Frank PTI,
formed by vacuum filtration using a Britt Dynamic Drainage Jar (Frank PTI, Birkenau, Germany).Birkenau, Germany).
Thesetup
The setupused
usedforforsheet
sheetforming
formingisisshown
shownininFigure
Figure3.3.

Figure
Figure3.3.Equipment
Equipmentused
usedfor
forfines
finesand
andMFC
MFCsheet
sheetformation.
formation.

The Britt Dynamic Drainage Jar is equipped with a supporting plate, a 500-mesh screen (hole
The Britt Dynamic Drainage Jar is equipped with a supporting plate, a 500-mesh screen
diameter 20 μm), two filter papers, and a nitrocellulose membrane (DAWP29325 from Merck
(hole diameter 20 µm), two filter papers, and a nitrocellulose membrane (DAWP29325 from Merck
Chemicals and Life Science GesmbH, Darmstadt, Germany) with a pore size of 0.65 μm. The major
Chemicals and Life Science GesmbH, Darmstadt, Germany) with a pore size of 0.65 µm. The major
advantage of using the Britt Dynamic Drainage Jar as compared to a Büchner funnel is to improve
advantage of using the Britt Dynamic Drainage Jar as compared to a Büchner funnel is to improve
the fines and MFC sheet formation. In particular, the sandwich-like setup prevents the loss of fine
the fines and MFC sheet formation. In particular, the sandwich-like setup prevents the loss of fine
cellulosic material. After the filtration step, the membrane with the fines/MFC sheet on top is pre-
cellulosic material. After the filtration step, the membrane with the fines/MFC sheet on top is
dried in a Rapid-Köthen sheet dryer (Frank PTI, Birkenau, Germany) for about 20 s at 93 °C under
pre-dried in a Rapid-Köthen sheet dryer (Frank PTI, Birkenau, Germany) for about 20 s at 93 ◦ C under
vacuum. Then, the membrane is peeled off, and the neat fines/MFC sheets are dried for 10 min in the
vacuum. Then, the membrane is peeled off, and the neat fines/MFC sheets are dried for 10 min in the
Rapid-Köthen sheet dryer. The sheets are then stored in a climate room at 23 °C and 50% RH for least
Rapid-Köthen sheet dryer. The sheets are then stored in a climate room at 23 ◦ C and 50% RH for least
12 h prior to testing.
12 h prior to testing.
2.4. Sheet Testing
2.4. Sheet Testing
Air permeability (Bendtsen method, ISO 5636-3:2013), thickness, and apparent density (DIN EN
Air permeability (Bendtsen method, ISO 5636-3:2013), thickness, and apparent density
ISO 534:2011) were determined in order to get structural information of the sheets. Mechanical
(DIN EN ISO 534:2011) were determined in order to get structural information of the sheets.
properties such as the modulus of elasticity, breaking load, and strain to failure of the sheets were
Mechanical properties such as the modulus of elasticity, breaking load, and strain to failure of the
measured using the Z010 tensile tester from Zwick Roell (Ulm, Germany). For tensile testing, a testing
sheets were measured using the Z010 tensile tester from Zwick Roell (Ulm, Germany). For tensile
speed of 5 mm/min, a free clamping length of 50 mm, and strip width of 15 mm were used; eight to
testing, a testing speed of 5 mm/min, a free clamping length of 50 mm, and strip width of 15 mm were
ten strips per sample were tested.
used; eight to ten strips per sample were tested.
The surface roughness of the sheets was determined using the Bruker DekTak XT surface profiler
The surface roughness of the sheets was determined using the Bruker DekTak XT surface profiler
(Bruker Nano Surfaces Division, Tucson, AZ, USA). The needle scanning the sheets had a tip radius
(Bruker Nano Surfaces Division, Tucson, AZ, USA). The needle scanning the sheets had a tip radius of
of 12.5 μm, and a scan force of 0.03 mN. The length of the line scan was set to 2 mm.
12.5 µm, and a scan force of 0.03 mN. The length of the line scan was set to 2 mm.
For the atomic force microscopy (AFM) measurements, a Veeco Multimode Quadrax MM AFM
For the atomic force microscopy (AFM) measurements, a Veeco Multimode Quadrax MM AFM
(Bruker; Billerica, MA, USA) was used. The images were recorded in the tapping mode (non-contact
(Bruker; Billerica, MA, USA) was used. The images were recorded in the tapping mode (non-contact
mode), and silicon cantilevers (NCH-VS1-W, NanoWorld AG, Neuchatel, Switzerland) were used
mode), and silicon cantilevers (NCH-VS1-W, NanoWorld AG, Neuchatel, Switzerland) were used with
with an average spring constant of 42 N/m (Force Constant), and a resonance frequency of 281–296
an average spring constant of 42 N/m (Force Constant), and a resonance frequency of 281–296 kHz
kHz (Coating: none). All measurements were performed at room temperature and under an ambient
(Coating: none). All measurements were performed at room temperature and under an ambient
atmosphere. In addition, the surface of the handsheets was investigated using low voltage scanning
electron microscopy (LVSEM) with the high resolution scanning electron microscope Zeiss Ultra 55
(Zeiss, Oberkochen, Germany), and the Everhart–Thornley detector (ETD) [19]. A beam energy of
0.65 keV was used.
In order to determine the static contact angle, as well as the surface free energy of the sheets, a
DSA100 (Krüss GmbH, Hamburg, Germany) equipped with a T1E CCD camera (Newton, NJ, USA)
Polymers 2017, 9, 366 6 of 12

atmosphere. In addition, the surface of the handsheets was investigated using low voltage scanning
electron microscopy (LVSEM) with the high resolution scanning electron microscope Zeiss Ultra 55
(Zeiss, Oberkochen, Germany), and the Everhart–Thornley detector (ETD) [19]. A beam energy of
0.65 keV was used.
In order to determine the static contact angle, as well as the surface free energy of the sheets,
a DSA100 (Krüss GmbH, Hamburg, Germany) equipped with a T1E CCD camera (Newton, NJ, USA)
and the DSA1 v 1.90 software (Krüss GmbH, Hamburg, Germany) was used. 3 µL droplets of Milli-Q
water and diiodomethane were deposited on the surface of the sheets, and after 2 s an image was taken.
Ten replicates were performed. The contact angle was calculated according to the Young-Laplace
equation. The surface free energy was calculated according to the Owens-Wendt-Rabel-Kaelble
(OWRK) method.

3. Results and Discussion

3.1. Lignin Content and Fines/MFC Morphology

The results of the κ number measurements are shown in Table 2. As expected, fines from the
unbleached pulp, as well as from the mechanical pulp show higher lignin contents when compared
to the other materials. The high lignin content in the case of mechanical pulp fines is a result of
the production process. In contrast to chemical pulping, the fibers in this case are separated from
the wood matrix itself by a mechanical process with no removal of lignin. Furthermore, primary
fines from unbleached kraft pulp, and to some extent also from bleached sulfite pulp have a higher
κ number when compared to the secondary fines since they are derived from domains rich in lignin
(e.g., compound middle lamella).

Table 2. κ numbers of the different cellulosic materials.

Header κ Number
B PF sulfite pulp 3.4
B SF sulfite pulp 2.8
UB PF kraft pulp 75.1
UB SF kraft pulp 50.7
Fines MP 162.1
MFC 1 1.2
MFC 2 0.7
MFC 3 0.6

The mean particle size (see Table 3), expressed as CEDq2 is similar for all the samples.
Secondary fines, as well as the microfibrillated cellulose samples MFC 2 and MFC 3 show the smallest
particle size. Some caution is needed regarding these results, as the resolution of the used L & W
instrument might lead to the effect that particles in the sub-micron range just are not detected. Primary
fines from unbleached kraft pulp and MFC 1 contain the largest particles. From the results, one
might conclude that the pulp fines, especially secondary fines, and MFC, can be compared in terms
of particle size, even though the two MFC samples (MFC 1 and MFC 3) have been prepared using
homogenizers, when compared to the refining of pulp to produce secondary fines using a Valley beater.
Taipale et al. [20] also already pointed out that the fines fraction of pulps exhibit properties similar
to MFC.
Optical microscopy images of pulp fines (Figure 4) reveal that size measurement is not straight
forward since smaller fragments of microfibrillar fines might not be detected by the L & W Fiber
Tester, due to its limited resolution of 3.3 µm/pixel [4]. Therefore, these images contribute to a better
understanding regarding differences in fines morphology of the different materials. MP fines (a) contain
fragments of the fiber wall and fibrillar material. However, these fibrils are more or less isolated,
and do not form a network like structure. In contrast, chemical pulp fines (b–e) form fibrillar networks
Polymers 2017, 9, 366 7 of 12

with a hierarchical, branched morphology. In addition to fibrillar fines originating from the fiber wall,
primary fines (b,d) also contain rod shaped parenchyma and ray cells. These cells were fragmented
from the wood matrix in the pulping process.

Table 3. Mean particle size of pulp fines (fractionated using the pressure screen) and MFC samples
(as provided), measured with the L & W Fiber Tester Plus; resolution 3.3 µm/pixel.

Header CEDq2 (µm) *

Polymers 2017, 9, 366 B PF sulfite pulp 40.35 7 of 12

B SF sulfite pulp 34.59
understanding regarding differencesUB PFinkraft
finespulp
morphology 52.73
of the different materials. MP fines (a)
UB SF kraft pulp 33.04
contain fragments of the fiber wall and
Finesfibrillar
MP material.37.16
However, these fibrils are more or less
isolated, and do not form a network like structure.
MFC 1 In contrast,
52.11chemical pulp fines (b–e) form fibrillar
networks with a hierarchical, branchedMFCmorphology.
2 In addition
38.19 to fibrillar fines originating from the
MFC 3 29.84
fiber wall, primary fines (b,d) also contain rod shaped parenchyma and ray cells. These cells were
fragmented from the wood matrix in* the
CED:pulping
circle equivalent
process.diameter.

Figure 4.
Figure 4. Optical
Optical microscopy
microscopy images
images ofof (a)
(a) MP
MP fines;
fines; (b)
(b) UB
UB PF
PF kraft
kraft pulp;
pulp; (c)
(c) UB
UB SF
SF kraft
kraft pulp;
pulp;
(d) B PF sulfite pulp; (e) B SF sulfite pulp.
(d) B PF sulfite pulp; (e) B SF sulfite pulp.

3.2. Results
3.2. Results Sheet
Sheet Testing
Testing

3.2.1. Apparent
3.2.1. Apparent Density of the
Density of the Sheets
Sheets
Figure 55 summarizes
Figure summarizes the the results
results of
of the
the apparent
apparent density
density measurements
measurements of of the
the different
different sheets.
sheets.
The materials can be classified into three regimes of density. The lowest
The materials can be classified into three regimes of density. The lowest apparent density is determined apparent density is
determined for the fines sheets derived from mechanical pulp (ca.
− 3 500 kg·m
for the fines sheets derived from mechanical pulp (ca. 500 kg·m ). Mechanical pulp fines are known−3). Mechanical pulp fines

arebeknown
to stiffer,to be stiffer,
thereby thereby
showing showing
a lower a lower conformability,
conformability, which probably which probably
originates from originates from
the higher the
lignin
content. Furthermore, the bonding ability of this material is lower, resulting in a potentially morea
higher lignin content. Furthermore, the bonding ability of this material is lower, resulting in
potentially
porous sheetmore porous The
structure. sheetsecond
structure.
set The second set
of samples of samples
comprises comprises
of the of the sheets
sheets made from Bmade from
SF sulfite,
B SFthe
and sulfite,
UB PF and the pulps
kraft UB PF(ca.
kraft pulps kg
700–750 (ca.·m700–750
−3 ). Thekg·m
third−3).set
The third set
includes theincludes the Bthe
B PF sulfite, PFUBsulfite, the
SF kraft
UB SF kraft sheets, as well as the different MFC sheets (900–950
− 3 kg·m −3). Regarding the sulfite pulps,
sheets, as well as the different MFC sheets (900–950 kg·m ). Regarding the sulfite pulps, sheets from
sheets from
primary finesprimary
are denserfines arethose
than denser
madethan those
from made from
secondary fines.secondary
In contrast,fines.
for theIn unbleached
contrast, forkraft
the
unbleached kraft pulps, the secondary fines lead to denser sheets. These results
pulps, the secondary fines lead to denser sheets. These results could be qualitatively explained by the could be qualitatively
explainedmorphologies
different by the different morphologies
of the samples. Samples of thewith
samples.
a higher Samples
degreewith a higher
of coarse degree
graining of coarse
(B SF sulfite
graining (B SF sulfite and UP PF kraft) have a low density, while the other feature higher densities.
In addition, the high density of PF sulfite might be reasoned by the thinner cell walls when compared
to PF kraft and differences in chemical composition as well.
 Polymers 2017, 9, 366 8 of 12

and UP PF kraft) have a low density, while the other feature higher densities. In addition, the high
density of PF sulfite might be reasoned by the thinner cell walls when compared to PF kraft and
Polymers 2017, 9, 366
differences in chemical composition as well. 8 of 12

Figure 5. Apparent density of fines and MFC sheets.

Figure 5. Apparent density of fines and MFC sheets.

Apparent density data, however, have to be read with care. According to ISO 534:2011, apparent
Apparent density data, however, have to be read with care. According to ISO 534:2011, apparent
sheet density is determined by using a dead-weight micrometer, provided with two plane, parallel,
sheetcircular
density is determined by using a dead-weight micrometer, provided with two plane, parallel,
pressure faces, with one face having a diameter of 16.5 mm, between which the sheet is placed
circular pressure faces,Therefore,
for measurement. with onethe
face having aof
roughness diameter
the sheetofalso
16.5influences
mm, between which the
the thickness sheet is placed
measurement,
for measurement. Therefore, the roughness of the sheet also influences the thickness
and thus also the calculation of the apparent sheet density. Compressibility of the sheets also measurement,
might
and thus alsothe
influence thethickness
calculation of the apparent
measurement, sheet density.
as the pressure exertedCompressibility of the sheets
between the two pressure also might
faces during
influence the thickness
measurement measurement, as the pressure exerted between the two pressure faces during
is 50 kPa.
measurement is 50 kPa. (Bendtsen method) was 0 mL/min for all the sheets, with the exception of the
Air permeability
MP
Air fines sheets (15.5
permeability mL/min),method)
(Bendtsen indicatingwas
that0the sheets are
mL/min forclosed.
all the sheets, with the exception of the
MP fines sheets (15.5 mL/min), indicating that the sheets are closed.
3.2.2. Surface Morphology and Roughness of the Sheets
In order
3.2.2. Surface to evaluate and
Morphology whether the differences
Roughness of theinSheets
apparent density can be related to the morphology
of the different samples on the micro/nanoscale, the sheets were investigated by AFM in a dry state.
In order
Figure to evaluate
6 depicts whether
the amplitude images the(10differences in MFC
× 10 µm2 ). The apparent
samplesdensity can small
(a–c) show be related
features to
in the
morphology
the chosenofframe
the different samples
(10 × 10 µm 2 oninthe
), while themicro/nanoscale, the sheets
fines samples, fragments were
of fibers areinvestigated
visible. by AFM
in a dry In
state.
orderFigure 6 depicts
to evaluate thethese
whether amplitude images
observations can(10 × 10 μm ). atThe
2
be determined MFCscale,
a larger samples (a–c) show
profilometry
smallmeasurements withchosen
features in the a Bruker DekTak
frame (10XT× surface
10 μm2profiler
), while(scanning needle
in the fines dip 12.5 µm)
samples, were performed.
fragments of fibers are
Table 4 summarizes the findings on the determined RMS roughness of the paper sheets. Therefore,
visible.
profilometry allows for a differentiated picture of the morphology of the sheets. The MFC derived
sheets exhibit RMS values of 1.9 to 2.3 µm, while those from the other materials, with the exception of
SF kraft pulp fines, have higher roughness values.
From this data it can be seen that the density of the sheets can be correlated to some extent to their
RMS roughness. Besides the MFC sheets, the sheets from B PF sulfite and UB SF kraft pulps feature the
lowest RMS roughness among all the prepared fine sheets, and, in addition, they have a comparable
density as the MFC sheets.
Selected sheets (MP fines, MFC 2, and secondary fines from kraft and sulfite pulp) were also
investigated using low voltage scanning electron microscopy (LVSEM). A rather low magnification of
500× was chosen in order to visualize features in a similar scale to the needle used in profilometer
measurements presented in Table 4. The results presented in Figure 7 correlate to the measured RMS
data using profilometry.
 3.2.2. Surface Morphology and Roughness of the Sheets
In order to evaluate whether the differences in apparent density can be related to the
morphology of the different samples on the micro/nanoscale, the sheets were investigated by AFM
in a dry state. Figure 6 depicts the amplitude images (10 × 10 μm2). The MFC samples (a–c) show
small
Polymers features
2017, 9, 366 in the chosen frame (10 × 10 μm ), while in the fines samples, fragments of fibers are 9 of 12
2

visible.

Polymers 2017, 9, 366 9 of 12

In order to evaluate whether these observations can be determined at a larger scale, profilometry
measurements with a Bruker DekTak XT surface profiler (scanning needle dip 12.5 μm) were
performed. Table 4 summarizes the findings on the determined RMS roughness of the paper sheets.
Therefore, profilometry allows for a differentiated picture of the morphology of the sheets. The MFC
derived sheets exhibit RMS values of 1.9 to 2.3 μm, while those from the other materials, with the
exception of SF kraft pulp fines, have higher roughness values.

Table 4. RMS roughness of sheets prepared from fines and MFC determined by profilometry and
labels used in Figure 6.

Header RMS Roughness (µm) Label

B PF sulfite pulp 2.3 ± 0.1 a
FigureFigure 6. AFM
6. AFM Bamplitude
amplitude
SF sulfite images
images
pulp (10 (10×× 10 µm22, ,scale
10 μm 2.5 bar
scale 0.1= 2= μm)
± bar 2 µm)of sheets fromfrom
of sheets bdifferent sources.
different sources.
(a) B (a)
PFBsulfite
PF sulfite pulp;
UB
pulp; (b)
PF kraft
(b) B SFB SF
pulpsulfitepulp;
sulfite pulp;(c)
(c) UB
UB PFPF
3.0kraft
± 0.2pulp;
kraft pulp;(d)(d)
UBUB
SF SF
kraft pulp; (e) MP
c pulp;
kraft (e)fines;
MP fines;
(f) MFC
(f) MFC 1; (g)1; MFC
(g) UB
MFC
2;SF2; kraft
(h) (h)
MFC MFC 3. 3.
pulp 1.7 ± 0.2 d
Fines MP 3.4 ± 0.3 e
MFC 1 2.3 ± 0.3
Table 4. RMS roughness of sheets prepared from fines and MFC determined by profilometry f and labels
used in Figure 6. MFC 2 1.9 ± 0.3 g
MFC 3 2.3 ± 0.1 h

From this data it canHeader

be seen that the RMS Roughness
density (µm)can be correlated
of the sheets Label to some extent to
their RMS roughness. Besides
B PF sulfitethe MFC sheets, the
pulp 2.3sheets
± 0.1 from B PF sulfitea and UB SF kraft pulps
B SFroughness
feature the lowest RMS sulfite pulp 2.5 ± 0.1 fine sheets, and,bin addition, they have a
among all the prepared
comparable density UB PFMFC
as the kraft sheets.
pulp 3.0 ± 0.2 c
Selected sheets UB
(MPSFfines,
kraftMFC 1.7 ± 0.2
pulp 2, and secondary d sulfite pulp) were also
fines from kraft and
Fines MP
investigated using low voltage scanning electron 3.4 ± 0.3
microscopy e
(LVSEM). A rather low magnification
MFC 1 2.3 ± 0.3 f
of 500× was chosen in order to visualize features in a similar scale to the needle used in profilometer
MFC 2 1.9 ± 0.3 g
measurements presented in Table 4. The results presented in Figure 7 correlate to the measured RMS
MFC 3 2.3 ± 0.1 h
data using profilometry.

(a) (b)

(c) (d)

Figure 7. Low voltage scanning electron microscopy (LVSEM) images of sheets from different sources.
Figure 7. Low voltage scanning electron microscopy (LVSEM) images of sheets from different sources.
(a) MP fines; (b) MFC 2; (c) B SF sulfite pulp; (d) UB SF kraft pulp.
(a) MP fines; (b) MFC 2; (c) B SF sulfite pulp; (d) UB SF kraft pulp.
Polymers 2017, 9, 366 10 of 12

Polymers 2017, 9, 366 10 of 12

Polymers 2017, 9, 366 10 of 12
3.2.3. Mechanical Properties of the Sheets
3.2.3. Mechanical Properties of the Sheets
3.2.3. Mechanical
Figure 8 showsProperties of the Sheets
the stress-strain curves obtained from mechanical testing using a Zwick tensile
Figure 8 shows the stress-strain curves obtained from mechanical testing using a Zwick tensile
tester. The MFC sheets show the highest
Figure 8 shows the stress-strain curves stress-strain values,
obtained from followedtesting
mechanical by theusingsecondary
a Zwick fines from
tensile
tester. The MFC sheets show the highest stress-strain values, followed by the secondary fines from
unbleached
tester. The kraft
MFC pulp. When
sheets showcomparing
the highestthe results obtained
stress-strain values,for kraft and
followed sulfite
by the fines, it fines
secondary is apparent
from
unbleached kraft pulp. When comparing the results obtained for kraft and sulfite fines, it is apparent
thatunbleached
the well-known advantages
kraft pulp. of kraft pulp
When comparing over sulfite
the results obtainedpulp
for in strength
kraft and sulfiteare also
fines,observed when
it is apparent
that the well-known advantages of kraft pulp over sulfite pulp in strength are also observed when
that the well-known
comparing fines sheets. advantages
Due to of kraft
their more pulp over character,
fibrillar sulfite pulp in strength
secondary are also
fines show observed
for both when
pulps
comparing fines sheets. Due to their more fibrillar character, secondary fines show for both pulps a
comparing fines sheets.
a better Due to their compared
more fibrillar character, secondary fines show for both pulps a
better stress-strain behavior
stress-strain behavior when
when compared totoprimary
primaryfines,
fines, withthe
with thedifference
difference being
being more
more
better stress-strain
pronounced forfor
thethe behavior
kraft pulp when compared
fines. to primaryand fines, with the difference being morein
pronounced kraft pulp fines.Although
Althoughsulfite,
sulfite,kraft,
kraft, andMFC
MFCfines
finesshow
showaa similar
similar behavior
behavior
pronounced
theinlinear forthus
the similar
kraft pulp fines. Although sulfite, kraft, andkraft
MFCfines
finesandshow athree
similar behavior
the linear region, thus similar E-modulus or stiffness, secondary kraft fines and all threesamples
region, E-modulus or stiffness, secondary all MFC MFC
in
exhibit the linear
more region,
strainmore thus
before similar
breaking. E-modulus or stiffness, secondary kraft fines and all three MFC
samples exhibit strain before breaking.
samples exhibit more strain before breaking.

Figure
Figure Stress-strain
8. 8. Stress-straincurves
curvesofoffines
finesand
andMFC
MFC sheets
sheets (v
(v =
= 55 mm/min,
mm/min,a afree
freeclamping
clamping length:
length: 50 50
mm,mm,
Figure
strip width: 8. Stress-strain
15 mm). curves of fines and MFC sheets (v = 5 mm/min, a free clamping length: 50 mm,
strip width: 15 mm).
strip width: 15 mm).
Handsheetsprepared
Handsheets preparedfromfromthe
the mechanical pulppulp fines have a significantly lower breaking load
Handsheets prepared from themechanical
mechanical pulp fines
fines have
have a a significantly lower
significantly lower breaking
breaking load
load
and
and breaking
breaking stresswhen
stress whencompared
comparedto tothe
the other
other materials.
materials. This
This isisdue
due totothe
thelower
lowerbonding
bonding ability
ability
and breaking stress when compared to the other materials. This is due to the lower bonding ability
due
due to to higher
higher lignincontent,
lignin content, as wellas as the lower
lower sheet density this
thismaterial
materialachieves (see Figure 5). 5).
due to higher lignin content,asaswell
well asthethe lowersheet
sheet density
density this material achieves
achieves (see
(see Figure
Figure 5).
The
TheThe lower
lower stress
stress can
cancan also
also partly
partly be attributed to the higher thickness of the mechanical pulp fines
lower stress also partlybebeattributed
attributedtotothe
thehigher
higher thickness
thickness of of the
the mechanical
mechanicalpulp pulpfines
fines
sheets, as with thickness, the load bearing area increases leading to lower breaking stresses.
sheets, as with
sheets, thickness,
as with thickness,thethe
load
loadbearing
bearingarea
areaincreases
increasesleading
leading toto lower breaking stresses.
lower breaking stresses.
3.2.4.
3.2.4. Contact
Contact AngleDeterminations
Angle Determinations and Surface
Surface Free Energy (SFE)
3.2.4. Contact Angle Determinationsand and SurfaceFree
FreeEnergy
Energy (SFE)
(SFE)
For all the sheets, static contact angles (SCA) have been determined using water and
ForForall all
thethesheets,
sheets,static
staticcontact
contact angles
angles (SCA)
(SCA) have
have been determined using
been determined using water
waterand and
diiodomethane. It can be clearly seen in Figure 9 that there are major differences in the wettability of
diiodomethane.
diiodomethane. It can bebe
It can clearly
clearlyseen
seenininFigure
Figure99that
that there
there are major differencesininthe
major differences thewettability
wettabilityofof
the different sheets with water.
the the
different sheets
different with
sheets water.
with water.
90
90
80
80
70
70
60
Contact angle H2O

60
Contact angle H2O

50
50
40
40
30
30
20
20
10
10
0 1

0 1

Figure 9. Static water contact angles of the paper sheets (Left) and the corresponding surface free
Figure 9. Static water contact angles of the paper sheets (Left) and the corresponding surface free
Figure 9. Static
energies water by
determined contact angles of the paper sheets(OWRK)approach
the Owens-Wendt-Rabel-Kaelble (Left) and the corresponding surface
(Right). As apolar free
liquid
energies determined by the Owens-Wendt-Rabel-Kaelble (OWRK)approach (Right). As apolar liquid
energies determined
diiodomethane wasby the Owens-Wendt-Rabel-Kaelble (OWRK)approach (Right). As apolar liquid
used.
diiodomethane was used.
diiodomethane was used.
Polymers 2017, 9, 366 11 of 12

As expected, bleaching of the pulp prior to sheet formation increases the hydrophilicity of the
paper sheets, mainly due to lignin removal. In fact, the determined Kappa numbers (see Table 2) match
very well the trends of the SCA with water, which means that the major part of the lignin is either
homogenously distributed in the fiber, or accumulated at the individual fiber surfaces. Consequently,
SCA’s with water decrease from ca. 70◦ , to below 50◦ . For all of the sheets prepared from MFC’s
(MFC 1–3), SCA with water are in this range as well. The same behavior is observed in the SFE where
the bleaching step increases the SFE of the sheets corresponding to a higher degree of hydrophilicity.

4. Conclusions
Sheet properties of primary and secondary pulp fines from different sources were compared
to MFC sheets, together with the use of novel equipment for fines separation in the kg scale from
paper pulps. The MFC samples tend to form the densest and smoothest sheets, also achieving the
highest strength. Sheets from secondary fines from unbleached kraft pulp exhibit structural and
mechanical properties coming close to MFC. The known differences between kraft and sulfite pulps
on the fiber level are also observable at the level of fines from these pulps. Sheets formed from
mechanical pulp fines exhibit a coarser surface, show the lowest apparent density, and significantly
lower stress-strain values. Hydrophilicity of the fines sheets is mainly depending on the chemical
composition, with higher lignin content imparting a more hydrophobic character.
Because of their wide spectrum of properties depending on pulp type and their similar character to
coarser MFC grades, fiber fines as a by-product of the paper and pulp industry might find applications
in various fields where presently the use of MFC grades is evaluated.

Acknowledgments: The K-Project Flippr2 is funded as part of Austrian COMET—Competence Centers for
Excellent Technologies promoted by BMVIT, BMWFJ, Styria and Carinthia. The COMET program is managed
by FFG. The authors further acknowledge the industrial partners Sappi Gratkorn, Zellstoff Pöls and Mondi
Frantschach for their financial support of the K-project Flippr2 .
Author Contributions: Wolfgang Johann Fischer conceived and designed the experiments. David Reishofer
performed and analyzed AFM, SCA and SFE experiments, Lukas Andreas Jagiello conceived and performed fines
separation from chemical and mechanical pulps, Romana Schmiedt, and Wolfgang Johann Fischer developed and
performed the sheet forming trials. Jerome Colson contributed MFC samples and data. Armin Zankel performed
LVSEM experiments. Melanie Mayr performed particle size analysis. Wolfgang Johann Fischer, Stefan Spirk,
Melanie Mayr, and Wolfgang Bauer analyzed the data and wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

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