J. Basic. Appl. Sci. Res.

, 1(11)2314-2318, 2011
2011, TextRoad Publication

ISSN 2090-4304
Journal of Basic and Applied
Scientific Research
www.textroad.com

Studying the Effect of Chemical Additives on Strength Properties of Recycled

Paper
Mohammad Nemati1, Nima Seyyedmohammadi1, Ahmad Samariha 1, and Mohammad Javad Shakouri2
1

Department of Wood and Paper, Science and Research Branch, Islamic Azad University, Tehran, Iran.
2
Young Researchers Club, Roudsar and Amlash Branch, Islamic Azad University, Roudsar, Iran.
ABSTRACT

Recycled paper, which is made from dried chemical fibers, has lower strength than paper made from
never dried fibers. By recycling, strength of paper was decreased. Since of drying the fibers, cellulose
gravity, water retention, flexibility and decreasing the accessible surfaces was understandable. Old
methods for increasing the paper strength were included both the dry-strength and refining the
recycled fibers. These methods increase the cost and energy consumption and also fibers shrink
during the refining and produce more fines and will cause problem for drainage and influence paper
production, but dry-strength additives can improve the paper strength. So we will have a review on
the role of chemical additives and confirmation of the mechanisms that control the effects of
papermaking additives on recycled paper.
KEYWORDS: cellulose gravity, water retention, dry-strength, papermaking.
INTRODUCTION
Waste paper is the most plentiful raw material in developed countries that are both producers and users of different
kinds of paper. In developed countries, paper production is based on wood pulp and waste paper. Proportion of these two
depends on the proportion of production and the amount of wood supply. At first, the main goal in paper recycling is
economical not environmental. Recycled papers should be able to compete with first hand papers (virgin) and have good
function in the process of transduction and usage. In some productions that paper is made of first hand pulp, recycled pulp
also has a good function. Type of original paper pulp has a great effect on recycling and recycled paper characteristics.
There are two kinds of waste paper, one of them is before and another one is after the use of customer. In this
section, most of our discussion is focused on the first kind. These papers include nonstandard produced papers,
unchangeable and unsalable ones that usually are called factory waste papers. Paper pieces from edge trimming and
transduction from ring to sheet are also the same group. This group includes printing house wastes, converters, bookbinders,
cardboard makers, box producers and some other things like that. For some people, these kind of papers are not waste
papers because have not proceeded the whole process of production. But in fact, these kinds of papers are important fiber
sources. Description of recycled papers in a way that involve different kinds of fibers is difficult. Regarding to the recycling
problems of printed and written papers, recycling factories like the waste papers with high quality that is not reached to the
customer. With progressing of the recycling technology, some existing problems will be resolved. However, many
researchers have studied the recycling problems like the way changing properties of pulp as a result of recycling methods,
the way resulting changes affect on papers made of them, etc. Studying methods were various and different. Raw materials
from recycling include not bleached pulps to mechanical pulps or even mixed of both [1]. In fact, it is clear that recycled
pulps as a substitute of virgin pulp, play an important role in paper industry, so that today in many countries around the
world, the paper industry cannot continue or exist without recycled pulps. This fact in regions like central, southern and
Western Europe is mainly because of economical reasons, but in countries like Japan, Korea, Taiwan or Mexico, another
reason is infrequency of wood sources to produce pulp [2].
The effect of recycling on paper properties
Resistance is one of the most important property of paper. Paper because of having ability to get used
appropriately, needs to have enough resistance. Paper resistance depends on the result of hydrogen bonds. Also bonds
resistance depends on the numbers and extension of bond areas. In recycling process, fibers irreversibly damage and this
damage has effect on the produced paper resistance properties. Experience shows that fiber resistance is only decreased by
intense heating. The reason is decreasing the number of between fiber bonds with aid of water molecules. However
chemical pulps lose more resistance in recycling than mechanical ones but basically are stronger than chemical ones. This
strength is because of chemical purity, behavior of mechanical pulps in recycling is totally different. Falling Resistance
*Corresponding Author: Mohammad Nemati, Department of Wood and Paper, Science and Research Branch, Islamic Azad University,
Tehran, Iran. E-mail: mhd_nemati@yahoo.com

2314

Nemati et al., 2011

properties after recycling these kinds of papers is lower and even in some cases increasing of one resistance property is
observed because in recycling process, some materials that obstacle formation and extension between the fiber bonds would
be deleted.
Kolofta et al (1999) studied the properties of recycled fibers in a way that study is under several processes and the
result was that continuous recycle of recycled papers were caused decreasing the fibrillation rate of the recycling fibers
areas and as a result it causes decreasing the potential of these fibers for between fibers connection an at last it causes
decreasing of paper resistance properties. Studies show that the essential reason of changes in paper properties is the
decreasing of bond ability in fibers. Maci suggests that at least a part of fiber formations potential loss is because of
decreasing of fiber wall swelling; Maci used WRV method (retention rate of water) for measuring the inner swelling of
fibers. He saw that WRV has decreased and he insisted on this point that the speed of decreasing in first and second times is
more than the other times. If recycled fibers refine in the limit that degree of fibers swelling reach to virgin fibers swelling,
produced paper resistance are equal in two conditions.
Cao et al [3] studied on the effect of pulp chemical compounds on recycling and saw that there is a strong relation
between pentosan or hemicellulose volume and resistance of recycled papers that has produced from those fibers [3].
Hawes and Doshi (1986) by studying the effect of repeated recycling on waste paper, find out that recycled fines give a little
help to paper resistance, but if pulp is refined, produced fines give less help to resistance than pervious fines. Produced fines
cause the reduction speed of dewatering, therefore in equal dewatering speed, the recycled pulp is weaker than virgin pulp
or in equal resistance, dewatering speed from recycled pulp is slower than virgin pulp [4]. Two important processing
properties that distinguish virgin pulps from recycled pulps are the amount of watering in dewatering section of paper
making machine and the formation of nonwoven web of paper and also different reactivity of those in proportion of
chemical additives.
Change in the quality of recycled pulp by different processes
When studying qualitative changes that happen by recycling process, they are not necessarily negative. Before
using recycled fibers its needed to make some changes in the quality of recycled pulp. Recycled pulp properties can be
changed with several processes like:
Refining:
The potential of paper making can change by refining to some extent similar to virgin pulps. In this condition the
main goal of refining is improvement the potential of making connections between fibers by re swelling in fiber wall.
Because this connection is missed during fiber drying. Achieving this goal was successful in laboratory refining and in semi
industrial and industrial levels. But recycled pulps have two weaknesses the first is that fibers length are shorter and the
second is that because of fines presence, freeness degree is lower. Of course freeness degree because of fines presence is
only special for mechanical recycled papers. Because freeness degree of chemical pulps increase after recycling. In equal
dewatering speed, refined recycled pulps are weaker than virgin pulps. If two kinds of recycled pulps and virgin ones were
refined until equal resistance, the speed of dewatering from recycled paper will be slower than virgin pulp, and this may
causes the reduction of production in paper making machine. Fiber refining will increase the amount of fines and decreasing
the length of fibers.
Preventing from hornification:
The term hornification is a technical term used in wood pulp and paper research literature that refers to the
stiffening of the polymer structure that takes place in lignocellulosic materials upon drying or water removal. When wood
pulp fibers are dried, the internal fibre volume shrinks, because of structural changes in wood pulp fibers. If fibers are
resuspended in water, the original water-swollen state is not regained [5]. The effect of hornification may be identified in
those physical paper or wood pulp properties that are related to hydration or swelling, such as burst or tensile properties.
Repeated recycles showed progressive variations in these properties for several cycles [6]. This concept, which was
introduced by G. Jayme in 1944, was originally expressed by the German word Verhornung[7], initially translated into
English as hornification, and later changed to hornification[5]. Jayme introduced the water retention value (WRV)
measurement by centrifugation and defined irreversible hornification as a decrease in WRV, expressed in percentage of the
original value [7]. The decrease in WRV was found to correlate in multiple recycling very well with fiber thickness as
measured from electron microscopic images, whereas no change in fiber width was detected after multiple fiber drying [89]. Further research showed that the process of drying of fibers causes a significant loss of large pores [10-13] and a
reduction of surface area [14-15]. Wet pressing has also been found to produce hornification [16-17].
Hornification is a technique that is mostly useing for analysis the differences that occur in fibers under impression of
recycling. Decreasing in water retention amount in fibers occur under impression of horrification. Basically recycling is a
method for removing the effects arising from horrification. As a result of mechanical function of refiner, fiber walls that have
formed hydrogen bonds during drying process will turn to form again. Hornification pulp shows less beat ability and produced
fibril materials are rougher, it shows that beating cannot return hornification completely but it can reduce it. One of the other

2315

J. Basic. Appl. Sci. Res., 1(11)2314-2318, 2011

methods is prevention the hornification, replacement of hydroxyl groups with other functional groups. In a way that fibrils in
neighbor walls do not bond together. Other method is fiber conversion will a material dissolved in water that is able to make
bonds with hydroxyl groups. This material prevents any close contact of micro fibrils together in drying process.
Mixing with virgin pulp:
Recycled pulp potential can advance by mixing virgin pulp with appropriate properties. Schwartz tagen and prezy
bizder found out that virgin pulp has a great effect in improvement properties of recycled pulp and the reason is that virgin
pulp has more active fibers and more active fines. They found out that adding refined virgin pulp to recycled pulp causes
more improvement in properties. (Studying these researchers has done on chemical pulp). Virgin fibers with high quality
also help in the other way to recycled pulps. And its that when these fibers were mixed with recycled fibers it causes the
increasing of the product quality in recycling again of paper.
Chemical additives:
Haward and Jowsay (1989) had some studies on the effect of adding cationic starch to recycled pulp and properties
of produced handmade paper, he saw that adding starch to recycled fibers leads to restoration lost bonds on surface of these
fibers and between bonds strength has increased and in the end it caused increasing of handmade papers resistance
properties to the level of virgin pulps [18] Probably most common additive for improvement of recycled pulp resistance is
cationic starch that mostly was added to wet part of paper making machine. Cationic starch does the bond strengthening by
improvement of bond strength to bonded surface of sheet. Also other methods have studied for increasing of recycled pulp
quality by adding chemical materials, which of course none of those have accepted generally.
Fiber fractionation:
This operation is doing when waste papers contain large amount of fiber kinds. In this operation, recycled pulps
were divided to two kinds of short and long fibers. There is a report from some Germany factories that is producing
corrugated board and liner test from kraft waste papers, it has been mentioned that pulp with screening is separated to two
parts of short and long and long fibers is refining separately, then by using one of these following programs the separated
fibers will be used again:
A: using two parts in producing two different kinds of papers in two separated machines.
B: using two parts in two layers or in more than two layers of one sheet.
C: remixing refined long fibers with not refined short fibers.
In this study it has been determined that from the sheet physical properties point and desirable use of energy, two first
methods have better function.
Chemical reconversion:
The other method is increasing quality by reconversion and using chemical materials. Diroo et al offered that for
delignification of recycled pulp that had been produced from several kinds of waste paper, oxygen care has been used. In
this method related properties of pulp resistance had a great improvement. Authors believe that ozone attacks to lignin and
more cellulose goes into reaction in spite of this, they assumed that the fiber surface in unknown way goes for chemical
changes. Because of high cost, this method cannot be used in commercial operations. In spite of this, generally with the
higher virgin pulp quality, recycled pulp quality and also mixed pulps that paper is made by those would be better [18].
In this subject, the effect of adding several kinds of chemical materials to virgin fibers of not bleached kraft pine tree that is
never dried has studied that maybe this adding obstacle from reducing of established resistance due to recycling [19-21].
DISCUSSION
The readiness of hydrolization of lactones by dilute alkaline solutions in oxycelluloses has been long recognized
[22-24]. The prevention of lactone formation in lignocellulosic materials was also proposed by the use of fairly alkaline
solutions [25] or lightly alkaline solutions of pH=8 [26-27] to be taken into account in alkalimetric studies of wood pulps
[28]. Because of the existence of a Donnan equilibrium [29], the pH of an external solution does not equal that of the
internal pores of lignocellulosic materials [30]. Therefore, either a multiple cyclic exposure to fresh alkaline solutions of
pH=8 or an external pressure sufficient to overcome the osmotic pressure between the external solution and the pore
solution is capable of a total reversal of the hornification process. The latter condition is actually proposed in US patent
4,385,172 [31].
The carboxyl groups contained in the wood pulp have been shown to have a major influence on the hornification of
kraft fibers. When in their hydrogen or acidic form, they promote more hornification [32] in such a way that the degree of
hornification increases with the growing number of carboxyl groups [33]. Conversely, a drying process that promotes
hornification generates a drop in carboxylic acid content in pulps [34]. It was also shown that the velocity of crosslinking
for a mechanical pulp during heat treatment increased with a periodate oxidation, which produced dialdehyde groups and
decreased with the reduction of the mechanical pulp with sodium borohydride. Finally, the activation energy involved in the

2316

Nemati et al., 2011

crosslinking process associated with hornification has been calculated and estimated between 80 and 130 kJ mol-1 [35], a
value very much higher than hydrogen bonding, typically between 10 and 40 kJ mol-1 [36].
Conclusions
Although perfectly diagnosed in terms of the occurrence of physical changes, the hornification phenomenon, in its
origin, has frequently been associated with the formation of irreversible or partially irreversible hydrogen bonding in wood
pulps or paper upon drying or water removal [37], thus overlooking research findings published in the 1950s and 1960s. The
chemical description of hornification based on hydrogen bond crosslinking raises a few questions. One finds puzzling that
certain polymeric intramolecular hydrogen bonds may be broken by water molecules, whereas some other hydrogen bonds
cannot. In relation to thermochemistry and chemical bond theory, it is hard to envision this description of hornification as a
coherent body of theory. The fact that the prevention or reduction of hornification is attained by alkaline solutions and
sodium borohydride, which are known to produce the cleavage of hemiacetal bonds (lactone bridges) in low polymer
carbohydrates, and that both the hydroxyl and carboxyl groups play a significant role in the degree of hornification clearly
suggest the ester linkage crosslinking nature of hornification. Furthermore, the esterification process of interlocking
lignocellulosic chains also explains the increase in strength properties and loss of hygroscopicity acquired after a treatment
with monochloroacetic acid for unbeaten pulps [38]. Therefore the authors conclude that a sufficiently varied source of
experimental data already exists to show that hornification is only a particular case of lactone bridge formation in
lignocellulosic materials.
In this perspective, water completely breaks hydrogen bonds in the amorphous part of the lignocellulose material,
especially between fibers. Conversely, the removal of water may bring the solid material in close proximity and regenerate
hydrogen bonding formation. Part of the existent carboxylic acid groups in the lignocellulosic structure will interact with
hydroxyl groups in neighbouring polymeric chains and establish covalent lactone bridges. These lactone bridges will further
condition the physical properties of the polymeric material such as a swelling decrease and an increase in wet strength
parameters (wet breaking load, wet stiffness or wet modulus of elasticity). This covalent crosslinking is not broken by water
molecules and will only disappear under the specific chemical conditions that reverse the lactone formation.
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.

10.
11.
12.
13.
14.
15.
16.
17.
18.

Mirshokraei S.A, 2001. Guide to Waste paper, Aeezizh Publication

Sixta H, 2006. Handbook of Pulp, vol.2. Wiley- VCH Verlag Gmbh .& Co. Weinbeim, Germany.
Cao B, U Tschirner and S Ramaswamy, 1998. Impact of pulp chemical composition on recycling.
Hawes H.F, and R.S Doshi, 1986. Fiber characterization Using Concal Microscopy the Effect of Recycling.
Minor JL 1994. Hornificationits origin and meaning. Progr Pap Recycling 3:9395 Oksanen T, Buchert J,
Viikari L 1997. The role of hemicelluloses in the hornification of bleached kraft pulps. Holzforschung 51:355360
Howard RC, 1990. The effects of recycling on paper quality. J Pulp Pap Sci 16:J143J149
Jayme G, 1944. Mikro-Quellungsmessungen an Zellstoffen. Wochenbl Papierfabr 6:187194
Bawden AD and RP Kibblewhite, 1995. Effects of multiple drying treatments on kraft fiber walls. In: Third
research forum on recycling. CPPA, Vancouver, pp 171177
Weise U, H Paulapuro, 1996. The effect of drying and re-wetting cycles on fiber swelling. In: Proc fourth
European workshop on lignocelluloses and pulp, advances in characterization and processing of wood, non-woody
and secondary fibers, Stresa, Italy, 811 September 1996, pp 389394
Stone JE, and AM Scallan, 1966. Influence of drying on the pore structures of the cell wall. In: Bolam F (ed)
Consolidation of the paper web. BPBMA, London, pp 145174
Stone JE, and AM Scallan, 1968. A structural model for the cell wall of water swollen wood pulp fibers based on
their accessibility to macromolecules. Cell Chem Technol 2:343358
Stone JE, Scallan AM, and B Abrahamson, 1968. Influence of beating on cell wall swelling and internal
fibrillation. Svensk Papperstidn 71:687694
Ehrnrooth EML, 1984. The swelling of dried and never-dried acid chlorite delignified fibers. Svensk Papperstidn
87:R74R77
Klungness JH, and DF Caufield, 1982. Mechanisms affecting fiber bonding during drying and aging of pulps.
TAPPI J 65:9497
Krassig H 1984. Struktur und Reaktivitat von Cellulose fasern. Papier 38:571582
Robertson AA. 1964. Some observations on the effects of drying papermaking fibers. Pulp Pap Mag Can 65:T161
T168
Maloney TC, Li TQ, Weise U, and H Paulapuro, 1997. Intra- and inter-fiber pore closure in wet pressing. Appita J
50:301306
Howard R, and C.J Jowsay, 1989. Effect of Cationic Starch on The Tensile Strength of Paper.

2317

J. Basic. Appl. Sci. Res., 1(11)2314-2318, 2011

19.
20.
21.
22.

23.
24.
25.

26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.

Zang 2004. effect of sugar addition before drying on wet- flexibility of redisperfed kraft Fibers
Hubbe, 2004. Refining to Over com Effect of Drying Unbleached Kraft Fiber in the Presence or Absence of Sugar
Venditti, 2001effect of chemical pretreatments of never-dried pulp on The Strength On Recycled Liner Board
Kaverzneva ED, Ivanov VI, AS Salova, 1952. Chemical transformations of the macromolecule of cellulose under
the action of oxidizing agents. VI. The presence in oxycelluloses of the groupings of carbonic esters and their
effect on the determination of uronic carboxylic groups. Izvest Akad Nauk SSSR, Otdel Khim Nauk, pp 185189
Samuelson O, and B Tornell, 1961. Influence of lactones upon the determination of carboxyl groups in cellulose.
Svensk Papperstidn 64:198203
Slavik I, Pasteka M, and M Kucerova, 1967. The behavior of lactone groups in cellulosic materials during the
determination of carboxyl groups by different methods. Faserforsch Textiltech 18:48
Stakheeva-Kaverzneva ED, and A.S Salova, 1951. Chemical changes of cellulose macromolecule under action of
oxidizing agents. IV. Lactone links in the macromolecule of oxycellulose and their effect on determination of
carbonyl groups by condensation with hydroxylamine. Izvest Akad Nauk SSSR, Otdel Khim Nauk 782790
Samuelson O, and B Tornell, 1961. Influence of lactones upon the determination of carboxyl groups in cellulose.
Svensk Papperstidn 64:198203
Wilson K, 1966. Determination of carboxyl groups in cellulose. Svensk Papperstidn 69:386390
Fernandes Diniz JMB, and A.D Pethybridge, 1995 Interfering lactone formation in alkalimetric studies of paper
wood pulps. Holzforschung 49:8183.
Fernandes Diniz JMB, 1996. Application of chemical equilibrium to wood pulps. Holzforschung 50:429433
Scallan AM, Katz S, and D.S Argyropoulos, 1989. Conductometric titration of cellulose fibers. In: Schuerch C (ed)
Cellulose and wood-chemistry and technology. Wiley, New York, pp 1457 1471
Yasnovsky VM, and D.M MacDonald 1983. Prevention of hornification of dissolving pulp. US Patent 4,385,172,
assigned to International Paper Co
Lindstrom T, and G Carlsson, 1982. The effect of carboxyl groups and their ionic form during drying on the
hornification of cellulose fibers. Svensk Papperstidn 85:R146R151
Racz I, and J Borsa, 1997. Swelling of carboxymethylated cellulose fibers. Cellulose 4:293303
Ruffini G, 1966. Improvement in bonding of wood pulps by the presence of acidic groups. Svensk Papperstidn
69:7276
Back EL. 1967. Thermal auto-crosslinking in cellulose material. Pulp Pap Mag Can 68:T165T171
Israelachvili JN. 1991. Intermolecular and surface forces, 2nd. Academic, San Diego, pp 123125
Smook GA, 1990. Hornification (keyword). In: Handbook of pulp & paper terminology. Angus Wilde, Vancouver,
p 135
Ruffini G, 1966. Improvement in bonding of wood pulps by the presence of acidic groups. Svensk Papperstidn
69:7276

2318