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Binderless Materials Obtained by Thermo-Compressive

Processing of Lignocellulosic Fibers: A Comprehensive
Review
Thibaud Pintiaux,a,b,c,* David Viet,c Virginie Vandenbossche,a,b Luc Rigal,a,b and
Antoine Rouilly a,b

As the worldwide demand for fuels and materials increases, fossil

resources are decreasing and global warming is a concern, and thus the
need for alternative solutions is high. In the industries of furniture and
housing, particleboards are interesting materials, as they reutilize wastes
from other industries (wood, agriculture) although they also rely on
chemical binders that are petroleum-based and toxic. A very promising
alternative is then clearly identified in finding ways to produce binderless
boards and associated materials. This review considers the state of the
art in the field of binderless board production, and other processes
making it possible to turn raw plant fibers into structural materials without
using any external chemistry. The mechanical properties and water
resistance are collected and compared. Identified chemistry changes
occurring during the thermo-compressive process are discussed with an
aim towards understanding of the mechanisms of cohesion.

Keywords: Natural plant fibers; Lignocellulosic materials; Bio-based materials; Agro-materials;

Compression-molding; Hot-pressing; Steam-treatment; Processing; Binderless; Particleboards

Contact information: a: Université de Toulouse. INP-ENSIACET. LCA (Laboratoire de Chimie Agro

industrielle).F 31030 Toulouse, France; b: INRA. UMR 1010 CAI. F 31030 Toulouse, France;
c: The Green Factory, 27 rue Chanez, 75016 Paris, France;
* Corresponding author: [email protected]

INTRODUCTION

Plant cell walls can be regarded as being high-end engineered nanoscale

composites basically composed of cellulose, lignin, and hemicelluloses (Rose 2003). The
supramolecular organization in the plant cell wall provides fascinating unique mechanical
properties (Niklas et al. 2006). Being the basic constituent of plants and because very few
organisms can degrade it, cellulose is the most widely occurring polymer on planet earth.
This polymer, made of β-1-4 linked D-hydroxyglucopyranose, has an extraordinarily
strong and rigid molecular design. The macroscopic Young’s modulus of plant cellulose
has been measured at 128 GPa (Page et al. 1971), which is higher than aluminium (70
GPa) or glass fibers (76 GPa) (Lo and Hoa 2006). The Young’s modulus of the crystal of
cellulose has been estimated to be 138 GPa (Sakurada et al. 1962). With low density and
high mechanical performance, it provides amazing strength and growth possibilities to
plants e.g. trees of 115 meters height (Sequoia sempervirens, Redwood national park,
California, USA) and 14.4 meters of diameter (Taxodium mucronatum, Arbol del Tul,
Oxaca, Mexico) can be found. Bamboo for example is a well known strong and fast-
growing plant widely used for small constructions in Asia. All civilizations have worked

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with wood or other plant materials to build tools, furniture, housing and many sorts of
goods.
A comparison of mechanical properties of synthetic and natural fibers is provided
in Table 1 (Eichhorn et al. 2001). It shows that plant fibers from diverse origins have
various mechanical properties, and they can in some cases compete with glass fibers, if
their relative densities are taken into consideration.

Table 1. Properties of Different Plant Fibers and Synthetic Fibers

Adapted from Eichhorn et al. (2001)

Furthermore, plant fibers are renewable, biodegradable, and safe for humans and
the environment. Using natural fibers instead of petroleum-based material or highly
consuming energy materials such as concrete or metal alloys is highly promising for
reducing the greenhouse effect and drastic climate change as well as reducing today’s
immense plastic waste environmental pollution (Lebreton et al. 2012).
Of course, interest in the use of natural fibers for materials has been motivated by
raising environmental consciousness. Such interest is revealed by the number of scientific
articles related to the introduction of plant fibers in composites using a classical
thermoplastic matrix (e.g. PVC, PE), which could also be partially bio-based (biobased
PE / PVC) to produce partially bio-based composites (Faruk et al. 2012), and also with a
biodegradable matrix to produce fully biodegradable composites (e.g. PLA, PBAT,
PHA's) even on a nano-scale (Reddy et al. 2013).
Another option is the use of plant fibers in a natural bio-based and biodegradable
matrix, e.g. starch or proteins to create a 100% bio-based and biodegradable composite
product (Rouilly and Rigal 2002). The fact that every thermoplastic biopolymer comes
from edible resources for humans has raised ethical problems because of the possible
land-use competition between food and convenience goods. Therefore, 100%
lignocellulosic fibers materials have to be designed based on agricultural wastes such as
cereals straws, oilseed cakes, etc.
Wood is also the input material of another huge industry: paper and its
derivatives, wherein water suspensions of wood fibers (pulps) are processed by squeezing
and drying. These “wet processes” will not be reviewed here. Neither will the
solubilization processes be considered (e.g. Lyocell, Carbamate), on which a review was
recently published (Fink et al. 2014). Pharmaceutical tablets that contain cellulose or

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starch as excipient will also be omitted because of the differences of process (ram
compression, cold processing to prevent damage to the active components, and size of the
molded objects).
Wood processing includes many technologies to cut, machine, deform, and
assemble pieces of wood without any additives, which produce eco-friendly materials,
until the wastes (saw dust, useless cuts, etc.) are considered. Saw dust and wood particles
are mainly burnt and composted (both disposal techniques released CO2 to the
atmosphere), but today they enter in processes to be assembled with binders or polymers
to form boards or more recently wood-polymer composites (WPC). Thermoset resins are
based on fossil resources, and most of them are formaldehyde-based, resulting in
emissions of formaldehyde from the final products with potential harm to customers and
the environment (Tunga Salthammer et al. 2010). The replacement of resins is also
considered for economical reasons because of the increasing part of resins in the cost of
particleboard production (Hashim et al. 2010), and even the recycling of the
formaldehyde from waste wood-based panels has been considered.
The situation just described provides reasons for the recent spike in researchers’
interest in pursuing studies on the processing of various plant materials into boards
without the use of additives, binders, resins, or chemical modifications, which is precisely
the aim of this literature review. This work will then focus on the thermo-compressive
processing of non-modified plant fibers without additives. Because of the interaction of
parameters one to the others and with water (which plays a major role) and because of the
high diversity of compositions and complicated structures of plant fibers, attention has
been placed on isolating parameters and effects, and precise research facts have been
reported here in order to highlight past achievements and future directions.

ABBREVIATIONS AND DEFINITIONS

Abbreviations
IB: Internal bonding.
MOR: modulus of rupture, equivalent to bending strength at break.
MOE: modulus of elasticity, equivalent to bending modulus, sometimes called
flexural Young’s modulus.
MC: moisture content
TS: thickness swelling, percentage of thickness increase, measured on a 50 mm
square sample after 24 h dipped in 20 °C water.
WA: water absorption, percentage of mass increase during the TS test.

Definitions
In the wood-based panel industry, particleboard (PB) products mainly are made
from wood particles (chips) recycled from wastes that are glued together with petroleum-
based binders. Oriented strand boards (OSB) are quite similar but the wood particles that
compose them are bigger with a particular flat geometry, i.e. like flakes. Fiberboards
(FB) on the other hand, are made from wood fibers, thinner elements that have been first
separated in a refiner. Finally, hardboards (HB) are produced from steam-exploded wood
particles and, if they are subjected to a wet process (Masonite) they do not require
binders.

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While the materials and processing conditions used in present-day production of
particleboard, strand board, and fibreboard products can provide a practical point of focus
for this review, some of the best evidence regarding the mechanisms underlying the
successful preparation of binderless board products can be found outside of the scope of
conventional wood-based panel manufacturing. Indeed, most of the literature gathered
during the preparation of this review did not employ wood and had experimental
conditions that would not fit the standards of wood-based panels (e.g. higher density,
longer pressing time, and higher temperature). This article focuses on collecting the
technological possibilities to produce self-bonded lignocellulosic materials and
explanations about the selfbonding mechanisms, for which it is important to take into
consideration all types of boards and confront the results (e.g. differences and
commonality between steam pretreatment, steam injection, and no-steam processing).
The mechanisms of cohesion in the different types of binderless boards are assumed to be
comparable; thus, when possible, the term "binderless particleboards" (no refining) have
been used as well as "binderless fiberboard" when a refining step was present. If reported
panels do not fit in a category, or when the elements concern all types of boards, the
generic term "boards" has been used.
In addition, a distinction will be made between steam-pretreated binderless
boards, which in most cases are indeed in the fiberboards type, and those which are not.
Most of the examples that enter the category of "non steamed" boards would be in the
particleboards type.
Usually boards are "pressed" (at low pressure) and 3D objects are "molded" (at
higher pressure) but, because the mechanisms of cohesion are discussed against pressure
and since selfbonding of "pressed" and "molded" materials relies on the same physico-
chemical phenomena, the term "molded" will thus be used for comparison when needed.
Delamination refers to the creation of cracks in compressed materials due to
excessive steam production within the specimen. Delamination most probably occurs at
high temperature and moisture content (MC) when pressure is released within the
specimens. An extreme case of delamination can make the materials explode upon
depressurization of a mold. Delamination is a casually identified limit in binderless board
production and is further discussed in the paper.

TABLE OF CONTENTS

1915 Introduction
1917 Abbreviations and definitions
1919 History of binderless compression-molded plant materials
1919 Overview of the mechanical properties and water resistance of self-bonded materials
obtained by thermo-compressive processing of plant fibers
1924 Effects of plant materials origin on the molded specimens
1927 The use of steam in plant material processing
1933 Thermo-compressive process parameters vs. properties of molded specimens
1944 Physico-chemical changes and mechanisms of cohesion in self-bonded thermo-
compressed plant materials
1954 Conclusions and future directions
1956 References cited

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HISTORY OF BINDERLESS COMPRESSION-MOLDED PLANT MATERIALS

Binderless boards were born with the Masonite® process (Mason 1928). William
H. Mason invented a process for producing wood fibers hardboards, using a steam
pretreatment step. The chemo-mechanical action inherent in the pretreatment released
components from the fibers on their surface to form an in situ glue. For historical reasons,
because of the close interaction of plant fibers and moisture and the very similar
chemistry changes occurring upon steam treatment and during hot pressing, steam
processing will be considered in this review.
Later, a patent of Runkel and Jost (1956) described a process called Thermodyn
for producing binderless boards from plant material without requiring steam. The
inventors described two stages in the process: during the first step, degradation gases are
produced from plant materials under heat and pressure, and these serve as hydrolyzing
agents to produce binders from the plant materials. This first step is very much like
Mason's steam treatment, although it occurs in the mold. In a second step that could be
separated, the material is molded into the desired shape. Some details are missing in the
patent. For example no problems are mentioned concerning steam delamination,
rheological behaviour, mechanical properties, or water resistance. Runkel and Jost
reported "physical, colloidal, chemical changes of the cell wall components, leading to
some sort of thermoplasticity of the material occurring under compression, heat, and in
the presence of a little moisture", and there is no doubt that these phenomena are keys to
understand the moldability of 100% natural fibers. The interest in this process was
probably not sufficient in comparison to petroleum-based thermoplastics so unfortunately
the Thermodyn process did not leave behind an imperishable memory.
More recently, Mobarak et al. (1982) published what is today' oldest available
academic paper on binderless boards made from unmodified natural plant materials
(Mobarak et al. 1982). The paper starts with a very nice overview on the older scientific
works that are in Russian and German, and most of them not easily available. They have
not been taken into consideration for this review.

AN OVERVIEW OF THE MECHANICAL PROPERTIES AND WATER

RESISTANCE OF SELF-BONDED MATERIALS OBTAINED BY THERMO-
COMPRESSIVE PROCESSING OF PLANT FIBERS

Mechanical Properties of Self-Bonded Thermo-Compressed Plant Materials

The concept behind binderless molded objects probably appeared with the idea of
avoiding the use of environmentally harmful binders. It is reasonable to assume that at
first, available production tools (pressing machines) were used; therefore, a first "boards"
category can be made, for which the process uses available and relatively low pressure.
Researchers working on binderless boards have the standard properties of wood-based
panels as reference and not the processing conditions. Most of the time, the idea of
binderless boards research is to reach the industrial wood–based panels properties (with
adhesive) without using binders. However, the higher temperatures and much longer
times required to meet quality standards may fall outside of the norms for commercial
production.

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Table 2. Summary Table of Mechanical Performances of Binderless Boards and Compared Properties Obtained by Steam
Pretreatment, Steam Injection Pressing and Without Treatment.*

Note: An asterix (*) in the density line means that target density is reported and not the actual density measured.

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Boards-type, low pressure molding
Mechanical properties of boards are commonly expressed with the use of three
variables, the modulus of rupture (MOR), the modulus of elasticity (MOE), and internal
bond (IB). Somehow, these three parameters are correlated. Plant materials do not
produce rubber-like materials (high MOR and low MOE), and the IB is also somehow
correlated with the bending properties. As the most common usage of boards (e.g.
flooring, furniture) relies on strength of the boards, the MOR is the first criterion.
Table 2 presents a quick comparison of the performances of steam-pretreated,
steam-injection pressed, and non-treated-materials binderless boards. All of the values
reported in this table come from the highest MOR obtained by researchers, with the MOE
and IB reported on the same specimen. It can be observed that steam pretreatment always
produces relatively strong products with decent MOR, whereas direct hot pressing
without any treatment of the starting materials can produce either low or high mechanical
properties. This basically means that the molding of natural fibers without any treatment
is more sensitive to the nature of starting material. Some materials would be suitable for
direct molding and do not need steam treatment, whereas some others would require it.

High pressure, plastic-substitute type, cellulose processing

Research involving new materials as well as the need for understanding the
chemical changes and processing possibilities of lignocellulosic materials have led some
researchers to work at higher pressure. In this review, the "high pressure" range would
start at around 30 MPa. But more than the value, "high pressure" is defined by the intent
from the authors to mold products towards the creation of new materials, with higher
density and properties, usually at a smaller scale. This would not be with the idea of
producing boards, but more likely plastic materials, which potentially can be three-
dimensional, extrusion tests, or transfer molding. Raw lignocellulosic materials have been
processed at high pressure (Miki et al. 2003), sometimes together with steam (Miki et al.
2007a; Takahashi et al. 2010), and pure cellulose compression molding was also studied
(Nilsson et al. 2010; Rampinelli et al. 2010; Zhang et al. 2012; Pintiaux et al. 2013;
Privas et al. 2013). The “ECAP” process (Equal Channel Angular Pressing) of Zhang et
al. (2012) comes from metallurgy and involves the material being subjected to high shear
stress; this approach is comparable to transfer molding as experimented by Miki et al.
(Yamashita et al. 2007) yet quite different from compaction molding (low and high
pressure), wherein shear is limited. The influence of shear is an interesting parameter,
however not very much described in molding, but well known in the wood welding
process from the group of Pizzi et al. (Gfeller et al. 2003).
Obviously, as can be seen in Table 3, high pressure can result in considerably
higher MOR than low-pressure molding, and the resulting densities fall in a narrow range
of 1.4 to 1.5 g/cm3. Results obtained on pure cellulose are quite disappointing compared
to lignocellulosic materials unless the material has been refined (micro-fibrillation).

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Table 3. Summary Table of Mechanical Performances of High Pressure Molding
Experiments for Producing Self-bonded Plant Materials

Water Resistance of Self-bonded Thermo-compressed Plant Materials

Water resistance is classically evaluated by measuring the water absorption and
thickness swelling of 5x5 cm specimen samples, which is convenient for comparisons.
Different standards are to be found in different parts of the world. The European system
(EN standards), for example, is quite complicated. TS requirements are specific,
depending on the type of panel (particleboards P1 to P7, EN 309 – medium density
fiberboard, EN 622-5 – oriented strand board types 1 to 4, EN 300). Particleboards of
type 3 to 7 have requirements of TS depending on specifications (humid environment or
not). Medium density fiberboard and oriented strand board also have increasing
specification of resistance against water, and all the values required by the standards vary
as a function of the boards’ thickness. Japanese standards, however, are much more
convenient, requiring that any type of boards should have a TS lower than 12%
(according to JIS A 5908 2003). The explanation for application of such a broad standard
probably arises from the very humid Japanese weather. The 12% maximum TS from the
Japanese standards is found as a reference in many publications and has been reported
here in Table 4. In this table, it can be observed that binderless boards have difficulties to
achieve water resistances good enough to pass the standards. The use of steam, however,
appears to significantly increase the water resistance.
Okuda and Sato (2004) reported that the mechanical properties of their binderless
boards made from kenaf core became reduced to (only) 1/3 of their dry value when
placed in wet conditions (Fig. 1) for specimens in the high range of IB. Another
promising value of 87% was reported upon high-temperature molding of bagasse
(Nonaka et al. 2013). Mechanical properties in the wet state are very rarely reported, and
these two examples are actually excellent values; sometimes, water resistance tests (TS /
WA) are not even reported because the specimens swelled and broke down in water.

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Table 4. Summary Table of Water Resistances of Self-bonded Thermo-compressed Plant Materials and Comparison Between
Steam Pretreatement, Steam Injection and Without Steam*

Note: An asterisk (*) in the density line means that target density is reported and not the actual density measured

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Fig. 1. Comparison between dry and wet mechanical properties (Okuda and Sato 2004,
republished with the kind permission of the Japan Wood Research Society)

THE EFFECTS OF PLANT MATERIALS ORIGIN ON THE MOLDED

SPECIMENS

Reported Molded Materials

The effect of the nature of plant material is a very delicate parameter to study
because materials and methods are rarely comparable between different studies reported
in the literature, and most of the time researchers tend to focus on just one plant. Also,
comparison focusing on one plant from one study to another cannot be considered 100%
reliable, as plant varieties, harvesting season, growing sites, etc. will create heterogeneity
(Saito et al. 2013).
Mason indicated that the Masonite disintegration process could work with pretty
much whatever "ligno-cellulose material" (Mason 1926a). Then for molding Masonite®,
it is reported that lignin is necessary for cohesion; therefore only materials containing
sufficient amounts of lignin after steam explosion would be suitable (Mason 1928).
Although wood is the only material present in the examples given in their patent,
Runkel and Jost (1956), considered that whatever "substances of vegetable origin which
contain resinogene groups and active carbonyl compounds or which can form such
groups" could be molded without using a pretreatment. On the other hand, Anglès et al.
(2001) mentioned that boards from non-pretreated residual softwood could not be
molded, and thus steam pretreatment was needed. Other wood materials were
successfully molded using steam pretreatment (Suchsland et al. 1987) or not (Ando and
Sato 2010). The groups of Miki and Takahashi also investigated the possibility of
molding wood at high pressure using steam (Miki et al. 2003; Takahashi et al. 2009) and
bulk bamboo (Yamashita et al. 2007). Also, cedar wood, bamboo rice straw, Ginkgo
biloba leaves, and coffee bean residues were densified into pellet fuels by high pressure
molding (Matsuura et al. 2012).
The oil palm tree is a vastly studied biomass. Suzuki et al. (1998) and Laemsak et
al. (2000) molded steam-exploded particles of oil palm tree fronds, and Nadhari et al.

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(2013) studied trunk particles treated in an autoclave. Different parts of oil palm tree
(Hashim et al. 2011a) and date palm tree (Saadaoui et al. 2013) were also molded without
steam.
The pith fraction of sugarcane bagasse was successfully molded without steam
treatment, and satisfactorily results were obtained (Mobarak et al. 1982; Widyorini et al.
2005a).
Kenaf core is another extensively studied material that was successfully molded
without steam (Okuda and Sato 2004) and also using steam injection pressing, which
made it possible to obtain low-density boards (Xu et al. 2004).
Miscanthus and banana bunches were also molded into boards with the help of
steam pretreatment (Quintana et al. 2009; Velasquez et al. 2003).
As a conclusion, no general trend can be extracted from these results. The
availability of waste plant material in one region often appears to guide the selection of
materials to be studied and comparisons between plants remains rare.

Different Parts of Plants

Type of plant tissue, cell wall structure and composition
Hashim et al. (2011a) compared the moldability of different plant tissues from the
oil palm tree. In the same processing conditions, without pretreatment, the bark and
leaves performed poorly, while fronds and trunk were much better. Bark cells had thick
and rigid cell walls and were not deformable enough to be molded. In contrast,
parenchyma is a spongy tissue of plants, consisting of living cells with a high lumen to
cell wall dimension; this structure was claimed to be responsible for good molding
capacity of fronds and core part of the trunk of oil palm tree. Consistent results were also
reported on date palm tree (Saadaoui et al. 2013).
Mobarak et al. (1982) also observed that bagasse pith (parenchyma cells) had
better molding capacity than depithed bagasse (less parenchyma cells). Also the pith part
reacted to pressure (higher pressure increased the bending strength), although depithed
bagasse had the same poor properties with higher pressure. The same conclusions were
reported on kenaf core (Okuda and Sato 2004) or coconut husk (van Dam et al. 2004a).
On the other hand, it was shown that whatever the conditions, sugi heartwood had
more than twice better mechanical properties compared with sugi sapwood on 1 mm
powder binderless boards processed without steam (Ando and Sato 2010). Heartwood is
the center, older, tougher part of the trunk, constituted of dead cells of higher lignin
content. This result appears quite contradictory compared to the previous ones unless
chemical differences (probably lignin and extractives) are considered. No difference was
observed between heartwood and sapwood when ground to 10 μm and used as a binder
for plywood for what was concluded that the grinding treatment cancelled the differences
of cell wall structure.

Particle geometry and the need of steam treatment

A comparison of hot pressing and steam injection pressing on the parenchyma
part (pith) and non-parenchyma part (rind) of bagasse showed no effect of steam for the
pith fraction but a positive effect of steam for the rind fraction (Widyorini et al. 2005a).
This would explain the results of many researchers, who necessarily employed steam for
molding non-parenchyma tissue, and also the good properties and many studies showing
a high interest for kenaf core and other parenchyma-rich parts of plants.

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Remnants of storage polymers and agroindustrial by-products
Different agricultural or industrial plant residues are to be found in different
countries, but a certain attention can been directed towards agroindustrial byproducts that
would contain significant amounts of storage polymers, namely starch and proteins.
Hashim et al. for instance worked on oil palm tree residues containing small amounts of
starch. They first managed to obtain satisfactory mechanical properties using strands of 3
to 5 cm long, and the SEM photographs showed an homogeneous blend of the cells and
melted and compressed starch granules (Hashim et al. 2010). In a second study on
different parts of oil palm tree, the IB correlated well to the starch content; starch was
able to melt and provide a matrix effect, bonding the fibers together in a composite
material (Hashim et al. 2011a). The starch granules were seen to fill the cell voids,
sometimes unmelted in the compressed material even at an elevated temperature of
200 °C; nevertheless, they were able to provide a bonding effect (Hashim et al. 2011b;
Lamaming et al. 2013). The melting of starch granules was confirmed after the materials
had been steam-pretreated and molded at 220 °C (Nadhari et al. 2013) or 180 °C (Saari et
al. 2014). The effect of starch as thermoplastic in situ binder has been reported to be
significantly lower than sugars upon molding (Lamaming et al. 2013). Another example
is to be found in the papers of Evon et al. (2010, 2012) who worked on sunflower cake,
(which contains proteins) and reported on thermocompressive molding of sunflower cake,
and that 3-D molding is easily accessible due to the thermoplastic behaviour of proteins.
In this case, studied material is truly an agroindustrial byproduct, wherein the thermo-
mechanical extraction of sunflower oil may play a role. Binderless boards were also
successfully molded on jatropha seed oil cake (Hidayat et al. 2014).

Mixing / structural associations

Reports on mixing of materials are rare, and so are reports based on structural
association of several plants. For instance, in order to counter-balance the poor flexural
properties of bark fibers, Gao et al. (2011) introduced a mix of wood fibers (30%) and
bark (70%) and tested different structural associations. They concluded that a
homogeneous mixture added lot of strength compared to the control (100% bark), but the
highest mechanical properties were achieved when they sandwiched bark between two
layers of wood fibers. When using such a construction, the MOR and MOE were almost
doubled compared with the control.

Contribution of lignin to water resistance

Many authors have made the hypothesis that lignin, on account of its hydrophobic
nature, was responsible for most of the water resistance observed on specimens (e.g.
Howard and Sandborn 1937; van Dam et al. 2004a; Okuda and Sato 2004). The addition
of lignin was reported to drastically increase water resistance, which supports the
previous hypothesis (Anglès et al. 2001). Additionally, it has sometimes been observed
that lignin degradation was correlated with a decrease of TS, showing that hydrophobic
degradation products could work as native lignin; such observations could also support a
hypothesis proposed by Ito et al. (1998b) to the effect that lignin was not responsible for
the dimensional stability triggered by the high-severity steam pressing treatment. Also,
the link with steam treatment could be made, as it was reported that steam treatment
increased the relative lignin content by degradation of other components, and the
correlation to the increase of lignin was made with an improvement of the mechanical
properties (Quintana et al. 2009). More elements about this are reported later.

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Contribution of hemicelluloses to water sensitivity
The fact that hemicelluloses must be eliminated for better water resistance was
already mentioned in the pioneering works of Mason. The reduction of hemicelluloses
content was performed because of a washing step prior to steam explosion, which effect
was later confirmed by others (Howard and Sandborn 1937; Suchsland et al. 1987;
Nadhari et al. 2013; Saadaoui et al. 2013).
Steam pretreatment and hot water extraction have been widely studied as a way to
improve water properties of classical adhesive containing wood-based panels (Hsu et al.
1988). This effect relies on an improved deformability of wood particles and reduction of
springback effect, both of which mainly can be attributed to the reduction of
hemicellulose content (Pelaez-Samaniego et al. 2014a). Comparable results were
obtained in binderless pressing (Anglès et al. 2001). The hypothesis was also formulated
that hemicelluloses’ bonding effect could be responsible for water sensitivity of the
molded products because of the hydrophilic nature of such bonds (Okuda and Sato 2004).
Finally, in the same way as the increase of lignin, the link between severity of
pretreatment and a decrease of the relative content of hemicelluloses was made (Fig. 2),
and a correlation was established with an increase of the water resistance (Velasquez et
al. 2003). The correlation between a decrease of TS and hemicelluloses content was
verified by others ( Widyorini et al. 2005b; Quintana et al. 2009), which could possibly
explain the improvement of water resistance observed by Ito et al. (1998a,b).

Fig. 2. Correlation between loss of hemicelluloses and improvement of water resistance in

binderless fiberboards, WA on the left (steam exploded miscanthus, adapted from Velasquez et
al. 2003), TS on the right (steam exploded banana bunch, adapted from Quintana et al. 2009).

THE USE OF STEAM IN PLANT MATERIAL PROCESSING

The first widespread usage of steam treatment for producing materials from
natural fibers was in the manufacture of Masonite® (Mason 1928). Mason developed an
apparatus called the Masonite gun (Mason 1926a, b) within which wood chips are steam
pressurized during a certain time before rapidly releasing the pressure, and the material
through a nozzle. A mechanical effect that breaks the structure of the fibers and leads to
what is described as a defibrated and fluffy state is produced, cell walls are damaged, and
inner plant cell wall chemical components made more accessible.
Steam-exploded wood fibers were processed into wet processed hardboard
without binders, and Masonite® was industrially produced. Multiple applications were

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possible due to its high density, low cost, and relatively good water resistance. The
product was also known as isorel, hernit, karlit, torex, or treetex. It was already claimed
in the patent that lignin and its accessibility were responsible for good mechanical
cohesion and water resistance of the materials (Mason 1928).
The steam pressure, in the range of a few MPa (Table 5), is directly linked to its
temperature. So basically, time and temperature (or pressure) are the two main
parameters. A higher pressure and/or a longer time will produce more "changes" in the
natural fibers, for which "severity" is a consensus term. Different materials can be
produced by varying the severity (Mason et al. 1937). The time – temperature
equivalence is described in the patent (Table 5), but it is also mentioned that a critical
temperature should be reached.
The low energy requirements and eco-compatibility of steam explosion made it an
interesting process for other applications than binderless boards, for instance for
reinforcing the water resistance of the adhesive based panels (Hsu et al. 1988; Pelaez-
Samaniego et al. 2013). Steam treatment was reported to increase the ethanol yield, lignin
solubilisation (Bundhoo et al. 2013), and also biogas yield production (up to 40%)
despite some negative effects due to the generation of compounds inhibitory to micro-
organisms (Zheng et al. 2014).

Table 5. First Report of a Time-Temperature Equivalence for Steam

Pretreatement adapted from US patent 1,824,221

(adapted from Mason et al. 1937)

Later, the time – temperature of treatment equivalence was formalized, and a

combining variable called "severity factor" was created for more convenient comparison
(Overend et al. 1987). This severity factor (also called R0) has the following expression:

(1)
The consideration of the log R0 imposes the prerequisite of the time - temperature
equivalence, which remained an hypothesis that was questioned (Velasquez et al. 2003).
There are basically two ways of using steam in the processing of binderless 100%
plant fibers materials:
 As a pretreatment on the starting material separately from the pressing stage: In
this case the very large majority of research works employed Mason's steam
explosion approach (Mason 1926a; Suchsland et al. 1987; Velasquez et al. 2003).
Some groups used a simple steam pretreatment in an autoclave without the
mechanical effect of steam explosion, (Howard and Sandborn 1937; Takahashi et

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al. 2009; Nadhari et al. 2013). Others used steam in addition to more mechanical
refining processes using disks or rolls ( Xu et al. 2003; Gao et al. 2011).
 As a processing aid, integrated in the pressing process, using a steam atmosphere
surrounding a pressing machine (Ito et al. 1998b; Widyorini et al. 2005c; Miki et
al. 2007a) or injecting steam in the mold during pressing (Xu et al. 2003).
The benefits of steam treatment as a first step are often reported to be tremendous
with respect to the mechanical properties. Anglès et al. (1999) for instance reported that
steam-treated biomass succeeded, whereas non-treated biomass compressed materials
were so weak they could not even be tested.

The Use of Steam as a Pretreatment: Effects and Optimal Conditions on

Molded Specimens
Mild severity optimum for strength

Optimal values of pretreatment (in order to maximize the MOR) are reported in
Table 6, which shows that the average optimal value for log R0 is about 4. Except for the
last two examples in Table 6, the optimal value was uniform, despite the fact that
different plant materials were being studied, including hardwood (Suchsland et al. 1987;
Takahashi et al. 2010), fronds of oil palm tree ( Suzuki et al. 1998; Laemsak and Okuma
2000; Nadhari et al. 2013), softwood (Anglès et al. 2001; Gao et al. 2011), and
Miscanthus (Salvado et al. 2003; Velasquez et al. 2003), etc.
Velasquez et al. (2003) optimized temperature and time separately, and concluded
that a lower temperature of pretreatment (200 °C) and long time (6 min, log R0 = 3.72)
were the best conditions, and in doing so questioned the time - temperature equivalence
(Overend et al. 1987). The pretreatment step was seen to have a higher impact than the
other parameters during the compression-molding, statistically. Using the same
methodology, similar conclusions were reported on steam pretreated banana bunches
binderless boards, and it was also observed that higher severity led to a decrease of the
bending properties (Quintana et al. 2009).

Table 6. Summary Table of Optimal Steam Pretreatment Severity for Producing

Self-bonded Materials

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High severity decreases MOR and MOE but is positive for IB and water resistance
Some papers have reported that severe conditions of pretreatment lead to lower
bending properties (Suchsland et al. 1987; Suzuki et al. 1998; Laemsak and Okuma
2000). Suchsland et al. (1987) also reported that high severity of pretreatment appeared to
increase the bonding ability, but the hypothesis was made that the shortening of the fibers
could hinder this effect, which would explain a decrease on the bending properties. The
mechanism was clarified later, with the measurement of a reduced cellulose content and
lower degree of polymerization, which made it possible to conclude that the partial
hydrolysis of cellulose caused by an excessive severity of treatment was responsible for
the lower mechanical properties (Anglès et al. 2001). Later, the IB was actually
confirmed to be maximized at high severity of pretreatment, and a higher proportion of
fine particles produced during pretreatment at high severity was suggested as an
explanation to higher IB values (Velasquez et al. 2003). Low temperature of pretreatment
was claimed to preserve the integrity of the fibers during pretreatment, although high
temperature during the pressing stage for a short time was seen to be the best strategy for
triggering the bonds without degrading the material too much. This was verified by
optimization experiments, which were conducted to achieve a maximum IB for higher
values of severity than for MOR / MOE, with the maximum value of 3.7 MPa (245 °C)
for 7.3 min (log R0 = 5.13) (Salvado et al. 2003). Consistent results were obtained on
banana bunches, wherein the IB was also demonstrated to be statistically dependent only
on the pretreatment severity (in related experimental conditions) (Quintana et al. 2009).
The maximum IB would be with a pretreatment severity factor of 3.55, which is lower
than values reported by the other authors. The same kinds of results were reported using a
steam-pressurized disk refiner, for which high pretreatment severity maximized the IB,
while at the same time the MOR was decreased (Xu et al. 2006).
Positive effects of steam explosion on the water resistance is a classic of the
adhesive bonded panels (Sekino et al. 2005). Mason reported good properties of
Masonite (binderless hardboard) against water (Mason 1928), and had another patent on a
more intensive use of steam explosion to produce water-resistant materials (Mason et al.
1937). The highest severity levels of pretreatment are uniformly reported to confer the
highest water resistance (thus lowest TS and WA values). There is certainly a link to
establish between self-bonding ability (IB values) and the water resistance (WA and TS
values), as the optimal parameters for these variables are similar.
Unsurprisingly, steam autoclave treatment was also reported to provide good
water resistance. A steam temperature of 180 °C was reported to have a high impact,
although further increase of temperature did slightly further increase the water resistance
(Takahashi et al. 2010). In a lower range of temperature treatment, Nadhari et al. (2013)
also reported the improvement of autoclave treatment on water resistance but concluded
that optimal conditions of treatment should be 120 °C and 46 min.

Steam pretreatment, flow behaviour, and molding capability

Steam pretreatment has also been considered as a way to dramatically increase the
flow capability of plant materials, which is of great interest towards the production of
objects of complicated forms in high pressure molding experiments.
A temperature higher than 160 °C made it possible to measure the flow ability of
Japanese beech using a commercial capillary rheometer. The fluidity increased with
temperature of pretreatment until 200 °C (Takahashi et al. 2009). Steaming temperature
was demonstrated to first allow flow and secondly to lower the temperature at which the

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flow occurs. It was demonstrated that 200 °C was an optimal temperature to impart
fluidity, and the material could be made to flow at only 9.8 MPa of extrusion pressure. At
180 °C of treatment, 29.4 MPa of pressure were needed to trigger flow. More generally,
the lower the temperature of steaming, the higher has to be the pressure to trigger the
ability to flow. A limit of temperature may exist, considering that the results at 220 °C
were worse than those at 200 °C. The same conclusion was reached regarding the time of
pretreatment, and the authors concluded that 10 min were sufficient at 200 °C to trigger
fluidity but increasing this time increased the temperature required for flow.
In a later study, Takahashi et al. (2010) correlated these results with the bending
properties of their boards, which showed that molding in conditions over the flowing
temperature / pressure of the material enhanced all of the mechanical properties that were
considered.

Steam as a Processing Aid: Effects and Optimal Conditions

Steam atmosphere pressing
The steam atmosphere pressing technique involves use of a pressing machine
wherein the mold is surrounded by a pressurized chamber where heated steam can be
injected. A prototype built by HISAKA corporation was used in several studies (e.g. Ito
et al. 1998a; Miki et al. 2007a). According to Miki et al. (2007a,b, 2008), the main
difference and explanation of the better results of steam atmosphere pressing results from
the steam saturation of air surrounding molded materials, which prevents moisture from
escaping. The prevention of loss of moisture during the molding process would therefore
be a major advantage to this technique. Steam atmosphere pressing also produced
improved water resistance (Ito et al. 1998a; Miki et al. 2008).
Widyorini et al (2005b) used a custom-designed porous metal pressing machine in
an autoclave chamber, gluing together 2 veneers of kenaf core. At 1 MPa (=> 180 °C) of
steam pressure, 10 min was an optimum bonding time, whereas at 1.5 MPa (=> 198 °C),
1 min was optimum. However, best mechanical bonding was achieved with 0.8 to 1 MPa
for 10 to 15 min.

Steam injection pressing

Steam atmosphere pressing entails a high cost of time and energy, as the whole
chamber needs to be pressurized and depressurized at each cycle. Alternatively, as
airtight molds are quite easy to build, another possibility is to inject steam directly into
the material while it is being pressed in the mold. Originally, steam injection pressing
was designed with the idea of maintaining a certain moisture inside the mat to improve
thermal conductivity and heat transfer from the plates (Kelly 1977; Back 1987).
The group of Kawai et al. (main results in Table 7) first studied the possibility of
molding binderless particleboards from kenaf core using a steam-injection pressing
method (Xu et al. 2003). Steam is injected in the mat at a pressure from 0.6 to 1 MPa
during the whole pressing stage. The IB and bending properties were reported to be much
higher compared to hot pressing, and these properties increased with steam pressure.
Treatment time had a low impact.

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Table 7. Examples of Conditions and Mechanical Properties of Steam Injection
Pressing Experiments for Production of Self-bonded Materials

In the first paper (Xu et al. 2003), delamination was reported in the case of higher
density boards, which was explained by a steam pressure imprisoned in the material that
exceeded the IB of the material, making the boards explode when opening the press.
Usually, binderless boards with density lower than 0.7 are not reported because of
insufficient mechanical properties. Yet, Xu et al. (2003) reported a good correlation
between density and the mechanical properties on binderless particleboards with density
from 0.35 to 0.65 g/cm3. Other results at lower density (0.15 to 0.3 g/cm3) (Xu et al.
2004) followed the same mathematical law as previously reported data, as can be seen in
Fig. 3. The addition of a pretreatment step with a steam-pressurized disk produced
fiberboards of very good properties with a low density of 0.5 g/cm3 (Xu et al. 2006).
Steam pressing produced specimens (bagasse binderless particleboards) with
values of TS mostly within the range 150 to 200% for conventional pressing and under
25% for materials made by steam pressing (Widyorini et al. 2005a). Dramatic benefits of
steam-injection pressing were reported elsewhere, e.g. for kenaf core binderless
particleboards (7.47% to 11% of TS were obtained compared to 169% without steam)
(Widyorini et al. 2005b; Xu et al. 2003).

Fig. 3. Example of correlation between MOR / MOE and density on a wide range of density from
Xu et al. (2004), where the dotted line is modeling from Xu et al. (2003); all results on steam
injected binderless particleboards from 5 mm chips of kenaf core. Figures republished with the
kind permission of the Japan Wood Research Society.

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Steam injection pressing, water resistance and boards’ thickness
In the industry of wood-based panels with adhesive, it is well known that the
volume / surface ratio has an effect on the WA and TS values. Under the same processing
conditions, thicker binderless boards are reported to have better TS values, and thinner
boards better WA ( Suzuki et al. 1998; Laemsak and Okuma 2000). The explanation
relies on the fact that the density gradient is generally less in thin boards, and higher
porosity on thicker boards allows more water to infiltrate without making the board swell,
which is why the comparison of water resistance is reliable only for boards of similar
thickness (Okuda and Sato 2006).
A consistent observation was made on low-density steam-injection pressed
binderless boards made from kenaf core, because of low density (0.25 g/cm3), high WA
values of 290% can be obtained on boards with very low TS of 9% (Xu et al. 2004),
which would pass the JIS standards if the standard covered this sort of special boards (JIS
A 5908, 2003).

THERMO-COMPRESSIVE PROCESS PARAMETERS AND THEIR EFFECT

ON PROPERTIES OF MOLDED SPECIMENS

Molding Pressure
Clarification of the relationship between pressure / density / target density
In the industry of wood-based panels, woods with bulk density lower than the
resulting particleboards should be used because there is a direct correlation between the
compression ratio and the boards strength (Kelly 1977). The purpose of pressing is to
bring the particles close to each other while the resin is being cured, which provides
thickness control. A "target density" is thus considered, when the mass of material
introduced in the mold and the thickness of the product are controlled. This can be
achieved, for example, in old presses by use of a metal frame (often called stop bars) that
prevents the pressing machine from compressing further than the desired thickness. In
classical particleboards, densities range from 0.6 to 0.7 g/cm3, while in classical
fiberboards, the values range from 0.65 to 0.85 g/cm3, for instance.
When no glue is used, the generation of an in-situ binder or some other
interparticle bonding phenomena is necessary for the product to keep its shape. In fact,
because of the lack of binder, a springback effect is often observed in much higher
proportions in binderless molding than in traditional resin-based wood-panels (Boon et
al. 2013). When unloading the press, the material expands, depending on whether its IB
is sufficiently high to retain the particles in their compressed form. Residual mechanical
stress remains and produces boards with final density lower than the targeted one. This is
why these have to be considered separately. The final densities observed in binderless
boards (in general) are higher, ranging from 0.8 to 1.35 g/cm3. In the industry of wood-
based panels with adhesives (thickness control), the initial pressure is impacting the
pressurization speed, that has an important effect on the vertical density profile (Kelly
1977), which is different than directly applied pressure. In this case, material can be
compressed more than the desired density, but with the springback effect, can obtain a
satisfactory density; a good explanation of this effect can be found in the work of Gao et
al. (2011).

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Effect of pressure: Board manufacture with target density
Common sense suggests that higher density boards will express better mechanical
properties (Suchsland et al. 1987). Even though this seems like an easy relationship,
some tricky results can be found in the literature. The same author, for instance, once
reported a good correlation (Anglès et al. 1999) and elsewhere did not observe any
correlation (Anglès et al. 2001) when boards with about the same density exhibited
variable mechanical performances. Also, in different studies of Hashim et al. (2010,
2011a,b), the authors suggested that increasing pressure could help to achieve better
bonding properties. But while 5 MPa of pressure was used in two studies (Hashim et al.
2010, 2011b), 12 MPa of pressure were later used (Hashim et al. 2011a), leading to better
properties. Possibly, the 5 MPa of pressure was not sufficient to reach the target density,
and the correlation should have been established based on density measurements. In
parallel, when the resulting density is correlated to the mechanical properties, very good
correlation has been observed (Ando and Sato 2009; Okuda and Sato 2004, 2006; Boon et
al. 2013). In one paper (Fig. 4), a non-linear correlation is reported; particleboards had

Fig. 4. Example of correlation between mechanical properties and density of boards. Left graph
(Okuda and Sato 2004) binderless particleboards from fine powder (53 µm) bagasse with a linear
correlation, right graph (Ando and Sato 2010) particleboards from Japanese cedar milled through
1 mm screen with a non-linear correlation. Republished with the kind permission of the Japan
Wood Research Society.

low properties at low density, but after a certain threshold of density, properties increased
and there was a linear correlation with density (Ando and Sato 2010). In this last case, an
explanation was proposed concerning the improvements of the properties coming from
the reduction of porosity when increasing density, which increased the thermal
conductivity. One parameter that has been barely studied is the pressurization speed,
which is well known to modify the vertical density profile, classical in the wood-based
panels with adhesive but almost never reported in articles concerning binderless molding.
For instance, it was reported that thicker binderless boards had much lower IB than thin
ones at comparable target density (0.8, 1, and 1.2 g/cm3) (Laemsak and Okuma 2000;
Suzuki et al. 1998) and the explanation to this probably resulted in the different density
profiles, induced by thickness differences.

Effect of directly applied pressure (pressure control)

As opposed to "target density" experiments, pressure directly applied on the
material without stopbars has been reported: Mobarak et al. (1982) were the first in the

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"modern area" to report on binderless boards. This paper first described a major effect of
pressure on binderless boards manufacturing from bagasse pith and reported that
mechanical strength of the boards was best at higher pressure (25.5 MPa), which is about
7 fold the usual pressure in the production of wood based panels (Fig. 5). An effect of
pressure was only observable for the pith part of bagasse, which is a non fibrous tissue
made of parenchyma cells. On every attempt, the density of the products was 1.35 g.cm-3
(about twice the usual density of traditional wood based particleboards), and it did not
increase with increasing molding pressure, showing that not only density (i.e.
compaction) was responsible for the mechanical properties. But in addition, pressure
must be triggering some destructuration and chemical reactions that bind the fibers
together (e.g. switching the glass temperature transitions of polymers, increasing
hydrolysis kinetics).

Fig. 5. Correlation between pressure and bending strength (adapted from Mobarak et al. 1982)

Ando and Sato (2009) used kenaf core powder as an adhesive in plywood
manufacture and showed that an increased pressure in the production of plywood gave
better shear strength, as well as a quicker heating up of the veneer stack when wood cells
were compressed. This was mainly caused by the significant increase of the board density
when working without stop bars and, hence, producing boards with accordingly lower
thickness at higher pressure. If the pressure exceeded a certain even higher limit,
delamination occurred, because steam pressure created during the hot press cycle was not
able to escape due to the tight material structure.

High-pressure molding
Very high pressures cause a certain flow behaviour of pure plant materials.
Extrusion tests on Japanese cedar powders were performed without any treatment (Miki
et al. 2003). It was demonstrated that extrusion was possible at pressures starting from 70
MPa, whereby extrusion pressures close to 300 MPa were achieved in these experiments.
Increasing temperature made it possible to reduce extrusion pressure. The relationship
between pressure and bulk density of the extruded product follows a logarithmic curve
with an inflexion point around 100 MPa (where obviously most of cell lumens have
already collapsed) and a density limit tending to 1.4 g/cm3 (Fig. 6), which is close to the
density of wood cell wall. The higher the pressure and the density, the higher are the
mechanical properties.

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Fig. 6. Correlation between extrusion pressure and density at high pressure extrusion of wood
powders (reproduced from Miki et al. 2003, with kind permission of the Japan Society of
Mechanical Engineers)

Later, wood powder was molded using high-pressure molding under a steam
atmosphere, and pressure had a clearly positive effect on the shock-resistance properties
(dynamic bending or Charpy impact) (Miki et al. 2007a), whereas static bending tests,
showed a limited effect (Miki et al. 2008). Figure 7 summarizes these two results. The
authors also noticed that using steam atmosphere pressing made it possible to reduce the
pressure needed to mold wood powder into materials and got excellent bending strength
up to 70 MPa with only 36.5 MPa of pressure. Using only 10 MPa of molding pressure
resulted in 60 MPa of bending strength specimens.

Fig. 7. Correlation between pressure and bending strength in dynamic test (gray dots) and static
(black squares) (adapted from Miki et al. 2007a and Miki et al. 2008)

Effect of pressure on pure cellulose molding

Recent papers have reported pure cellulose compression molding trials and the
effect of pressing pressure. Within the range of 40 to 200 MPa, an optimal at 120 MPa
was reported for maximizing bending strength (Rampinelli et al. 2010), whereas
elsewhere no statistical difference was observed between 134 and 267 MPa of pressure

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(Pintiaux et al. 2013). Good results with a cold / hot two stages process were reported
when using only 45 MPa of pressure (Nilsson et al. 2010). Pressing values from 0.7 to
2.5 GPa (Privas et al. 2013) were reported, but the researchers had to conclude that the
pressure range was too high to observe any significant effect. Thus, a pressure below 0.7
GPa was sufficient to achieve the maximum density.

Moisture Content
Natural fibers are highly hygroscopic, and the water content modifies structural
parameters such as crystallinity and lowers the glass transition temperature of its
polymers (Célino et al. 2014). It is therefore an essential parameter.
Historically, according to the patent of Mason (1937), MC should be adjusted to
5% before pressing. A coproduct of the Masonite process was reported to have an optimal
moisture content of 4% for molding (Howard and Sandborn 1937). Without using steam,
an optimal moisture for producing compression-molded objects is reported as being
between 5 and 25% and preferably between 8 and 17%, according to the patent of Runkel
and Jost (1956), which suggests that moisture can be adjusted in a wide range. It was then
reported that increasing MC had a negative impact on the mechanical properties (Table
8), but a minimum moisture was necessary to successfully mold products from bagasse
(Mobarak et al. 1982).

Table 8. Moisture Content and Effect on the Mechanical Properties of Molded

Bagasse Products (Density 1.34-1.36 g/cm3)

(Adapted from Mobarak et al. 1982)

Molding of dried (0% MC) plant material is generally unsuccessful, and many
papers have reported that there is a need for a minimum MC, which is 3% according to
Nadhari et al. (2013), but changing MC in the range ~10 to 30% seemed to have less
effect on the resulting mechanical properties ( Okuda et al. 2006a; Ando and Sato 2009).
Nevertheless, high MC was reported to trigger delamination due to steam accumulation in
the material during hot pressing (Ando and Sato 2009). The interaction between moisture
and temperature is very important; for instance, in a high temperature range (200 to 280
°C) the adjustment of MC to lower values (2 to 3%) produced good properties with a
maximum at 260 °C (Nonaka et al. 2013). In this study, the 200 °C values were quite low
because of the low MC. These last results can be compared with the classical process in
the production of industrial wood-based panels in which moisture is reduced in order to
prevent reactions with the resin. In the industry, moisture is known to be impacting the
density distribution which has never been studied in binderless boards experiments (Kelly
1977).
An increased MC was also reported to facilitate the flow ability of wood powders
(Miki et al. 2003) and bulk bamboo (Yamashita et al. 2007). Miki et al. (2003) also
demonstrated that the increase of moisture shifted the temperature at which the bending
strength was maximum: at 0 and 8% the optimum temperature was 195 °C, although at

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43% moisture 175 °C was the optimal temperature. Finally, higher moisture produced
significantly weaker materials.
The state of the plant cells has been reported to be different after extrusion
(transfer molding), based on SEM observations; the cells were barely observable and had
a "matrix" look, although with moisture the cells were still identifiable after molding
(Yamashita et al. 2007). Moisture was concluded to ease the separation of the cells
during flow testing at high pressure. The same observations was made later on different
materials (Yamashita et al. 2009).
Okuda and Sato (2006) reported that the water resistance increased drastically
with increasing MC of the initial material, because of a lower softening point of lignin
(plasticization) and better heat transfer (Xu et al. 2006). The MC effect also was
diminished at higher temperature of molding because softening point of lignin was
already reached (Okuda and Sato 2006). However higher MC caused delamination on 0.7
g/cm3 density boards (although 0.5 g/cm3 density boards were correct).
Concerning pure cellulose molding, the authors’ group has reported consistent
results. Dry cellulose performed poorly, whereas 6, 8, and 10% MC cellulose had good
and comparable mechanical properties (Pintiaux et al. 2013). Privas et al. (2013), on the
contrary, reported higher modulus for dry samples, suggesting that, with very high
pressure, moisture was prejudicial to the cohesion.

Temperature gradient, moisture, time and heat transfer

In the classical wood-based panels process, temperature is the energy source to
cure the resin. Moisture has the role of facilitating the heat transfer from the plates to the
inside of the mat and keeping the particles deformable (lower softening temperature of
wood polymers in presence of moisture) for adequate resin/wood particles-fibers contact
and target density (Kelly 1977). Temperature and moisture gradients exist inside the mat
which has been fully described in the industry standards but rarely reported in binderless
boards experiments (Bouajila et al. 2005). In the surface layers, a certain evaporation
takes place during the press cycle which permits to get close (~80%) to the plate
temperatures (i.e. skin effect), whereas in the core layer, temperature remains close to the
water evaporation temperature (depending on pressure, 105 to 115 °C). Increasing
pressing time increases the temperature inside the mat but the pressure increases, which
can cause delamination. The same way, moisture reduction will reduce steam pressure
but also heat transfer; this explains why these parameters have to be optimized together.
This has been done in thousands of papers in the wood-based panels with adhesive, but
characterization of such phenomena are still incomplete in the field of binderless boards
processing.

Temperature
Effect of pressing temperature on non-treated and steam treated materials
Temperature is often described as the most important factor in the production of
binderless natural fibers moldings (van Dam et al. 2004a). Thermal treatments are also
crucial in the improvement of properties of wood composites, adhesive containing wood-
based panels, and self-bonded plant materials (Pelaez-Samaniego et al. 2013).
As can be seen in Table 9 which summarizes the conditions for which highest
MOR was observed in different studies, research papers on non-steam treated binderless
boards and high pressure molding are often reporting an optimal temperature between
180 and 200 °C, except for Shen (1986), who's material contained a high proportion of

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free sugars and Nonaka et al. (2013), who lowered the MC. Over this favorable range of
temperatures, the mechanical properties are decreasing and/or delamination occurs (Ando
and Sato 2009, 2010; Hashim et al. 2011b).
Some reports have concluded that increasing temperature had a high impact on
increasing the IB of particleboards, which consequently led to the increase of the bending
properties ( Okuda and Sato 2004; Hashim et al. 2011b).
A high temperature of pressing was reported to increase the water resistance and
to be the most impactful molding parameter ( Anglès et al. 1999; Velasquez et al. 2003;
Ando and Sato 2009, 2010; Boon et al. 2013; Hashim et al. 2011b; Nadhari et al. 2013).
Better results than equivalent UF or UMF bonded boards were once reported (Okuda and
Sato 2006). The TS value went under 10%, which matches particleboards standards.

Table 9. List of Optimal Temperature as Reported in the Literature for Producing

Self-bonded Plant Materials Without Steam *

Note: An asterisk (*) in the process line indicates the presence of stop bars, Two asterisks (**) in
the density line means that the target density is reported and not the actual density measured.

A higher range of temperature have been reported for steam-pretreated plant

fibers (Table 10) than for non-treated materials. Low temperature molding processes are
reported only for steam-pretreated fibers. In the absence of pre-treatment, there is no or
reduced possibility to produce objects at low temperature of, for example, 125 °C (Suzuki
et al. 1998; Laemsak and Okuma 2000). Still, a high temperature of pressing is also
reported to have a positive impact on the mechanical properties of compressed specimens
after plant fibers have been steam treated (Anglès et al. 1999; Velasquez et al. 2003).
One report (Salvado et al. 2003) mentioned however that temperature had a limited
impact on the mechanical properties from 195 to 245 °C (which is still in a high range).

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Another report mentioned no effect of temperature on the IB but a drastic and positive
effect on the MOR (Nadhari et al. 2013). Confronting these results, it seems difficult to
present a general trend; also, for an unknown reason, most of the research studies on
steam pretreated material tended to use higher temperatures and reduced molding times
(the time / temperature of molding equivalence is a classic for standard panels
production).

Table 10. List of Optimal Temperature as Reported in the Literature for

Producing Self-bonded Plant Materials with Process Involving Steam

Note: An asterisk (*) in the process line indicates the presence of stop bars, Two asterisks (**) in
the density line means that the target density is reported and not the actual density measured.

As far as high pressure molding is concerned, temperature was demonstrated to

increase the flowability of wood powder but also increased the stiffness of the extruded
products, with a maximum reached at around 180 to 200 °C (Miki et al. 2003). The
thermal decomposition was thought to be responsible for better flowability during
extrusion (Yamashita et al. 2007). In the case of high-pressure molding under steam
atmosphere, 160 °C was reported as the optimum temperature (Miki et al. 2007a, 2007b,
2008). As for cellulose molding, optimal temperatures have been reported at around 160
to 180 °C (Nilsson et al. 2010; Rampinelli et al. 2010).

Delamination process a conjugated effect of temperature and moisture content

The 180 to 200 °C limit of pressing temperature, as reported previously, usually
comes from delamination. It could be density-dependent (Ando and Sato 2009) because
low-density products would have sufficient porosity for the steam to escape.
Delamination can occur in all sorts of plant material molding: particleboards, fiberboards,
and high pressure molding (Rampinelli et al. 2010). In cellulose high pressure molding,
the delamination limit was reported to be around 200 °C (Pintiaux et al. 2013). Similar
phenomenon was observed in high pressure extrusion of wood: lower density and lower
mechanical properties are reported, and SEM observations showed cracks and bubbles
(Miki et al. 2003).

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To some extent, pressure can be released in the process by using a degassing
phase, which is a classical procedure for standard panels production, described as a 3-
step-process (i.e. compression degassing compression) e.g. used by Anglès et al. (1999)
on steam exploded softwood for binderless fiberboards. The degassing phase made it
possible for some authors to mold at temperatures exceeding a previously established
temperature limit (Okuda and Sato 2006; Okuda et al. 2006a). With higher MC (20%) at
120 °C of pressing temperature, the degassing could not prevent delamination. This
showed that first, the degassing step is a limited solution, and secondly confirmed that the
delamination phenomenon is caused by an interaction between moisture and temperature
of pressing. The adequate control of MC and temperature and the understanding of their
interaction is a key parameter (Nonaka et al. 2013). It was also demonstrated that
sometimes cracks are not obvious (not observable on the outside of the material), and
MOE and MOR values can be high, whereas at the same time, IB can be drastically
reduced. Likewise, the water resistance and especially WA (increased) can be reduced
under such situations, because water can more easily infiltrate into the samples. This
observation is also a classic finding associated with standard panels production.
The cooling down of the specimen prior to releasing the pressure has been
reported to work for preventing delamination ( Yamashita et al. 2007; Miki et al. 2008).
In some cases the cooling step was not sufficient to prevent cracks and bubbles, which
were still observed on the materials. The cooling down of the mold between two pressing
cycles is obviously a marginal option, as it is time and energy consuming.
Some papers have reported the application of vacuum to boards before unloading
the pressure, which is easy in the case of a steam injection pressing apparatus, but the
results were not satisfactory (Widyorini et al. 2005a).

Pressing temperature and steam assisted molding

The examples of steam injection pressing all reported a molding temperature of
190 °C, but such results have been limited to a few publications, all from the same
research team. Actually, this value is the result of 1 MPa of injected steam pressure (183
°C) plus a few degrees in order to prevent the water for condensing in the mold (Xu et al.
2003).

Pressing temperature, time, and water resistance

The classic time / temperature equivalence suggests that the optimal pressing
conditions could be either a moderate temperature of molding during a long time or a
higher temperature for a short time. The effect of time was reported to decrease at high
temperature (Anglès et al. 1999). Elevated temperature is also reported to allow the
reduction of molding time at comparable board properties (Ando and Sato 2010). It was
also observed that higher temperature resulted in boards having lower density, which was
correlated to lower mechanical properties (Okuda and Sato 2006). But, this higher
temperature improved the mechanical properties in the humid state, despite the fact that
density was lower. More precisely, it was observed that increasing temperature led to
increasing the WA but reducing the TS; this indicates that bond quality was better with a
lower TS, but voids (cracks) were created in the inner structure, therefore increasing WA.
Overall, and in a way comparable to the severity of steam treatment, it can be observed
that optimal conditions for bonding (i.e. favoring the IB) will also maximize the water
resistance (Boon et al. 2013).

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Skin effect
A special effect on the surface of materials obtained by compression molding is
often reported ( Runkel and Jost 1956; Mobarak et al. 1982; Suzuki et al. 1998; Anglès et
al. 2001; Laemsak and Okuma 2000; Okuda and Sato 2004; Xu et al. 2004; Hashim et al.
2011b; Nadhari et al. 2013). The inner part of this kind of material appears rough and
mat-like, but the surfaces are, under certain conditions (elevated temperature but not
exclusively), smooth, plastic-like, and shiny. The vertical density profile is a classic from
the industry of wood-based panels with adhesive, but unfortunately it has been poorly
investigated in the research works concerning binderless molding.

Effect of temperature in the particular case of free sugars containing materials

A free sugars binding system requires 180 °C or more to achieve thermoset
bonding (Shen 1986), and higher temperature leads to the best mechanical properties and
water resistance of boards. According to Mobarak et al. (1982) and their trials on bagasse
pith, increasing temperature from 175 to 185 °C increased the bending strength by 9%
but lowered water resistance, which could be explained some delamination as observed
by many others. In this later paper, the best specimens had a WA of 11% and a TS of
7.5%, which are excellent values way over the average results. Sugar was also thought to
be responsible for the good properties of bagasse molded at high temperature and lower
MC (Nonaka et al. 2013). Consistently, the addition of sugars in oil palm trunk
particleboards was reported to drastically improve the properties with twice lower TS and
WA (Lamaming et al. 2013). Even more impressive, similar products were reported to be
resistant to boiling in water (Shen 1986). This very particular behavior is certainly
attributable to the in situ resin generated by reactions (decomposition and recondensation)
of free sugars induced by high temperature. These include thousands of reaction oligomer
products having up to 6 carbohydrates units and reactive furfural derivatives units (Golon
and Kuhnert 2012).

Effect of temperature in the particular case of bark

The binderless molding of bark has been successfully reported between 205 and
300 °C (Chow 1975; Mobarak et al. 1982). The molding of bark at "classical"
temperatures (180 °C) consistently produced boards with very low properties (Hashim et
al. 2011a). A more recent study reported 240 °C and 20 min as optimal conditions of
pressing refined spruce bark into boards, whereas 260 °C was the best temperature for
maximizing IB (Gao et al. 2011). These authors performed TGA analysis and showed
that temperature was responsible for a higher weight loss in the material during pressing
(up to 33%). In this paper, nothing more precise than “components were produced and
responsible for selfbonding” was mentioned, but if higher temperature is necessary for
molding bark parts, the explanation may be the high content in polyphenolic compounds
that can undergo radicular polymerization.
Elsewhere, tannins have been investigated to serve as a binder for particleboards:
Good results were reported with laccase-assisted oxidation of tannins, wherein
thermomechanical pulp was successfully bonded (Euring et al. 2011), and hydrolyzed
tannins were reported to perform better than condensed tannins (Widsten et al. 2009).
Ionic interaction and radical coupling were reported between tannins and wood fibers as
bonding mechanisms (Widsten and Kandelbauer 2014).

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Time
Time of molding is quite often reported to be an interesting parameter for
improving the mechanical properties, although it is tempting to try to reduce the time as
much as possible to increase production speed. Some reports indicated that increased time
is preferable for mechanical properties (Anglès et al. 1999) and water resistance ( Okuda
and Sato 2004; Nadhari et al. 2013), although a certain limit was reported to exist after 20
min in the bonding ability of kenaf core powder for a 4 mm plywood (Ando and Sato
2010). In contrast, some researchers have reported that a short time of molding was
preferable (Velasquez et al. 2003), which was associated with a high temperature of
molding. Other reports showed that time has a limited impact on the mechanical
properties (van Dam et al. 2004a), which is consistent with high pressure molding of
cellulose (Pintiaux et al. 2013). Another report mentioned 6 min to be an optimal time for
a 1 mm thick cellulose plates (Rampinelli et al. 2010).

Granulometry
Grinding is an energy-costly step, but lower particle size increases specific
surface area and accessibility to inner cell wall components, which is positive for
molding. Molding smaller particles also means that the strength of individual elements
has less effect, and the bonding between the particles is responsible for most of the
strength. Generally, reducing particle size is reported to have a positive effect on the
mechanical properties (Shen 1986; Okuda and Sato 2004). The good effect of steam
explosion could also partly rely on the generation of fines and global decrease of particle
size because of the treatment (Suchsland et al. 1987). Molding bigger particles was
confirmed to decrease the mechanical properties (Mobarak et al. 1982; Okuda and Sato
2006). Also, the introduction of bigger particles in fine powder was reported to degrade
the mechanical properties, which were then comparable to 100% bigger particles
(Mobarak et al. 1982).
Gao et al. (2011) obtained the best IB with finer particles (from 0.356 to 1 mm),
but larger particles (> 1 mm) gave rise to higher MOE and slightly higher MOR boards.
Consistent results were obtained elsewhere (Xu et al. 2006). The good adhesive strength
of very fine powder (10 μm) was reported (Ando and Sato 2009) to be better than 1 mm
particles, but the production of boards made of 10 μm powder failed (Ando and Sato
2010). This shows that a limit in the reduction of particle size may exist.
In some cases, bigger particles were reported to produce interesting properties
(Hashim et al. 2010; Saari et al. 2014). In this particular case, strands of several mm long
were compared to small particles (< 1 mm) under similar conditions of process and target
density, but only bending properties were tested. Elsewhere, better water resistance was
obtained from chips compared to powder under the same operating conditions (Okuda
and Sato 2006), but overall, few results can be found about the particle size effect.
Conditions favoring higher IB usually have been shown to increase water resistance, but
this seems not be the case for reduced particle size.
Concerning high pressure molding, Miki et al. (2003) demonstrated that higher
particle size needed more pressure to be extruded. However, the bending strength of the
products of 180 to 250 m (small particles) and 90 μm (powder) was not significantly
different. The effect of high shear on the material might be responsible for leaving no
effect of granulometry, as the particles were really deformed and rubbed against each
other. The same research group later reported an important result on the effect of
granulometry in a steam atmosphere pressing process. The very fine particles did not

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perform strongly, and an optimum was observable around 100 m particle size (Fig. 8,
Miki et al. 2007a). This somehow confirmed that a limit in reducing particle size would
exist for optimal properties.

Fig. 8. Effect of particle size on mechanical properties in high pressure molding under steam
atmosphere (adapted from Miki et al. 2007a)

THE PHYSICO-CHEMICAL CHANGES AND MECHANISMS OF COHESION IN

SELF-BONDED THERMO-COMPRESSED PLANT MATERIALS

The molding phase is usually conducted at air equilibrium MC (between 5 and

12% and often 8 to 10% MC with room equilibrium) and temperature over 100 °C; steam
is thus created in the mold. Chemical changes occurring during hot pressing can thus be
compared with steam pretreatments. The first thing to notice is that the molding time can
be very fast if material has been pretreated (Suchsland et al. 1987; Suzuki et al. 1998),
although short times of molding have not been reported on non-treated plant material.
The pretreatment, however, takes some time to operate, and both processes, pretreatment
+ molding, or molding without pretreatment, can take about the same time. Runkel and
Jost (1956) actually mentioned 2 phases in the molding of untreated natural fibers,
considering a first step of production of gases from the material and their action on the
material itself, and a second step of actual molding. The chemical modifications,
however, were not reported in these early publications. Recent results have been bringing
new data and highlights of these chemical changes occurring and help to explain the self
bonding ability of binderless plant materials which will be examined in this section.

Physical changes
Change of color
During steam explosion of plant materials, a change of color, darker with higher
severity of treatment, has been systematically reported, which suggests chemical changes
( Mason 1926a; Hsu et al. 1988; Anglès et al. 1999). The same phenomenon is also
observed as a result of an autoclave treatment (Takahashi et al. 2010) and on specimens
produced by steam atmosphere pressing (Miki et al. 2007a) and steam injection pressing
(Widyorini et al. 2005c). The same observations are made during classical compaction
molding, darker with higher temperature and time of molding (Runkel and Jost 1956;
Ando and Sato 2009; Boon et al. 2013). Obviously, the change of color is a sign of
degradation: the TGA analysis of plant fibers shows that hemicelluloses are the first to be
completely degraded (240 to 300 °C). Lignin starts to degrade at about the same

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temperature (240 °C), but its degradation slowly proceeds until 700 °C; cellulose on the
other hand degrades in a narrow range of 320 to 380 °C (Yang et al. 2007). The
degradation occurring during hot pressing or steam treatment takes place at much lower
temperature than the TGA results, but conditions are too different (pressure, moisture,
air) to conclude. Yet, degradation reactions and the change of colour are often associated
with better mechanical performance and water resistance and common explanation for
this is the generation of reactive compounds reacting on the fibers, with cross linking and
condensation reactions.

Steam treatment and defibration

Pretreatment with steam is called "steam explosion" and "wood disintegration"
(Mason 1926a, 1926b), "steam treatment" (Anglès et al. 1999; Velasquez et al. 2002,
2003), or a certain type of "pulping process" (Suchsland et al. 1987), which name
originates from the paper industry and the aspect of the fibers after treatment. Mason also
used the term of "fibration" of wood (Mason 1926a) and described a "highly divided
fibrous state" (Mason 1926b). The use of steam for defibrating has been since widely
developed as refining method (also in a thermo-mechanical refiner) for the production of
industrial wood-based panels (fiberboards and hardboards).
A low severity factor (e.g. 2.6) steam treatment does not bring any observable
difference from the original fiber to the steam pretreated, but a higher (e.g. 3.8) severity
factor produced fibers with similar length but smaller width, as can be seen in SEM
photographs of Anglès et al. (1999). An individual fiber will be turn into a network of
thinner single fibers with pretty much the same original length, thus increasing the aspect
ratio length to width (Xu et al. 2006). The defibration is time and temperature-dependent
and mild conditions are considered the best option, as the fibers were described as
becoming “long, light and fluffy” and not too much damaged.

Production of fines
After a Masonite gun treatment, 5 to 8% of fine solid material is discarded
because this material would create defects on the surface of the Masonite boards; this fine
material was molded and patented as a potential replacement for backelite (Howard and
Sandborn 1937). Suchsland et al. (1987) reported about average fibers length and fines
generation; steam treatment is not only increasing the aspect ratio, but also breaking
down the fibers assembly, generating smaller particles. As seen earlier in this review,
smaller particles (fines, i.e. ~ 0.2 mm and less) were seen to bring better performances
(Shen 1986; Okuda et al. 2006b) and more precisely the IB (Xu et al. 2006; Gao et al.
2011), which is consistent with the steam effect on fines generation.

Non-lignocellulosic Parts Chemical Changes and Effects

Weight loss, extractives, and elimination of degradation products
The weight loss occurring during conventional hot pressing has not been clearly
investigated, and it is in fact quite difficult to measure the weight loss due to degradation
separately from a MC change. Hydrolytic reactions producing acetic and forming acids
were reported (Mobarak et al. 1982), and autohydrolysis of plant materials has been
described as a result of acids generated from their own degradation (Li et al. 2007).
The presence of high amounts of extractives (in the leaves) was thought to be
prejudicial for mechanic performances, even if a high lignin content was measured
(Hashim et al. 2011a). The authors made the hypothesis that extractives (e.g. chlorophyll)

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could hinder the bonding mechanisms. Other reports showed that removal of extractives
prior to molding lowered the mechanical properties and the water resistance (Lamaming
et al. 2013; Saito et al. 2013).
According to the Masonite corporation patents (Howard and Sandborn 1937),
hemicelluloses are degraded with steam pretreatment, and products resulting from
degradation are water-soluble. Therefore they can be rinsed out, which increases the
strength and water-resistance of the products which is a classic of adhesive containing
wood-based panels or composites (Pelaez-Samaniego et al. 2013). Hsu et al. (1988)
reported that steam pre-treatment of wood chips increased the amount of water
extractives, and a correlation of the "total solubilization" and log R0 (scale for severity of
steam pretreatment) was established (Table 11) (Anglès et al. 2001). Consistent results
are found in other studies ( Widyorini et al. 2005b; Takahashi et al. 2010).

Table 11. Degradation and Weight Loss Measured upon Steam Pretreatment
Severity (adapted from Anglès et al. 2001)

A similar result was obtained with steam-injection pressing, and again the weight
loss was correlated with steam pressure and time, which was an indication of degradation
reactions during the treatment (Widyorini et al. 2005c). A correlation was also
established between IB and the weight loss (Xu et al. 2006).

Cellulose and Hemicelluloses Changes

Cellulose and hemicelluloses degradation
Hydrolysis reactions leading to partial depolymerization of hemicelluloses and
lignin are most likely to occur (Yang et al. 2007), and degradation products of
hemicelluloses and lignin are confirmed in the water extractives from steam pretreated
biomass (Sun et al. 2005). This was already mentioned in the work of Howard and
Sandborn (1937), Suzuki et al. (1998), Tanahashi (1990). This hypothesis was also made
for autoclave treatment of wood pieces (Ito et al. 1998a).
Actual data confirmed the effective degradation of hemicelluloses and the positive
correlation with severity upon steam explosion (Hsu et al. 1988; Quintana et al. 2009),
steam injection pressing (Xu et al. 2006) with confirmation of xylose being measured in
the water extractives (Widyorini et al. 2005b), and also concerning autoclave treatment
(Takahashi et al. 2010). Degradation of hemicelluloses was also confirmed for classical
hot pressing (Xu et al. 2006). For instance, Xu et al. (2006) measured 26.7% of
hemicelluloses on refined fibers, 25.5% on the fiberboard resulting from hot pressing, and
20.2% when using steam injection pressing.
Cellulose is also thought to be degraded during steam treatments. The relative
cellulose content was reported to decrease with increasing severity of steam explosion
(Anglès et al. 1999). The alteration of cellulose was also demonstrated in another study
(Anglès et al. 2001) where the DPv (viscosity measurements of the degree of
polymerization) was reported to decrease. Steam injection pressing was also reported to
decrease alpha cellulose content, even though glucose residues were not significantly

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more extracted (Widyorini et al. 2005b). Consistently, the decrease of holocellulose
content was reported using an autoclave treatment and confirmed as being positively
temperature dependant (Takahashi et al. 2010). Cellulose degradation was not always
observed, and some reports indicated a constant holocellulose content after steam
explosion (Quintana et al. 2009).

Correlation of cellulose and hemicelluloses content and the physical properties

The basic idea is that hemicelluloses and lignin can undergo glass transition and
will, hence, be responsible for the adhesion. Cellulose would not actively participate in
the molding but rather serve as “reinforcement” for the lignin/hemicellulose matrix (Saito
et al. 2013). But on the contrary, Ito et al. reported an important role of cellulose in the
mechanisms of cohesion especially for water resistance. Steam treatment was observed to
hydrolyze amorphous domains and turn cellulose crystal Iα into Iβ (Ito et al. 1998b). In a
second paper (Ito et al. 1998a) the authors concluded that steam treatment partially
hydrolyzed even paracrystalline region of cellulose and that novel crystals were
responsible for the shape fixation and water resistance. This findings were also confirmed
by Tanahashi (1990).

Furfural and hydroxymethyl furfural routes hypothesis

When weak acid or water at 130 to 170 °C is added to hydroxymethyl furfural,
polymerization occurs (Mobarak et al. 1982; Shen 1986); this reaction could take place
during hot pressing of natural fibers after some degradation of hemicelluloses, which is
an old and motivating hypothesis (Suzuki et al. 1998, Runkel and Jost 1956). The furfural
hypothesis has been often questioned and debated (Anglès et al. 1999; van Dam et al.
2004b). However, few reliable chemical analyses have been published so far.
Okuda and Sato (2004) added 5 to 15% of furfural in their binderless boards, and
they observed a small increase of IB. However, they could not prove a correlation
between IB and amount of furfural addition. In a further study the authors suggested that
furfural polymerization would not occur significantly (Okuda et al. 2006b).

Fig. 9. Furfural (and derivatives) content changes during steam pretreatment and molding
(adapted from Suzuki et al. 1998)

Figure 9 shows that 5-hydroxymethyl furfural (HMF) content increased with

pretreatment and was also higher in the board than in the steamed fibers (Suzuki et al.

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1998). These results tended to verify the furfural hypothesis for the pretreatment step, but
as furfural content increased after pressing, a possible polymerization remained uncertain.
New results were reported recently which confirmed the formation of furfural and HMF
during hot pressing from respectively pentoses and hexoses, and high temperature
pressing made the HMF react to form new products (Cristescu and Karlsson 2013;
Lamaming et al. 2013).

Lignin Changes
Lignin, according to Mason (1928), is the most important chemical for self-
bonding and for water resistance of fiber-based binderless molded objects. Mason
mentioned that during the molding operation, lignin melts and creates a welding effect.

Observation of lignin flow after steam pretreatment and matrix effect

The industrial thermomechanical refining process produce fibers bundles wherein
the surface of the fibers is covered by lignin; the wet hardboard production process takes
advantage of it by using lignin to form intra-fiber bonding (Back 1987). The explanation
to this is in the moisture temperature conditions of thermomechanical refining over the
softening point of lignin which preferably breaks wood structures within the lignin-rich
middle lamella (up to 70% lignin content), producing holocellulose-rich units (fibers)
encased in lignin (Irvine 1985). In binderless boards production, the use of steam-
exploded materials other than wood was explored to produce fiberboards-like materials
with the hypothesis of using lignin on surface of the fibers to create a matrix effect, the
same way than in wet processing of hardboard, but at lower target density and in dry
processing (Suzuki et al. 1998).
Lignin droplets were effectively observed on the surface of steam-treated fibers
(Anglès et al. 1999). These lignin droplets came from the coalescence of lignin resulting
from hydrolytic cleavage at high temperature which largely eliminates the
lignin/cellulose interface (Marchessault et al. 1982). Their size was evaluated to be in the
range 100 to 400 nm.
The conditions that made it possible to observe lignin on the surface of fibers also
produced the best IB on the binderless fiberboards (Anglès et al. 1999; Gao et al. 2011).
Consistently, a black matrix embedding the fibers, assumed to be the result of cross-
linking of degradation products of hemicelluloses and lignin, was observed as a results of
an autoclave treatment and during the pressing step; heat further allowed matrix
components to flow out of the cell wall to fill the gaps between the particles (Takahashi
et al. 2010). In the context of wood torrefaction study, recent results demonstrated that
liquid lignin intermediate (LLI) migrated from the middle lamella upon thermal treatment
and deposit on the fiber surface (Pelaez-Samaniego et al. 2014b).

Lignin modification / degradation

Lignin polymer is reported to obtain an increased polydispersity upon steam
treatment; the influence of refining temperature on the chemical changes on lignin is well
known (Marchessault et al. 1982). Other literature reports (e.g. Fig. 10) have indicated an
increasing lignin content (Klason method) with severity of pretreatment (defined page
1928) (Quintana et al. 2009; Takahashi et al. 2010; Lamaming et al. 2013).

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Fig. 10. Link between the increase of lignin content and pretreatment severity (adapted from
Quintana et al. 2009)

A particularly high Bjorkman yield (Björkman 1956) was reported after steam
pretreatment, which suggested an increase of the relative apparent lignin content,
including a lot of "esterified and etherified phenolic compounds" (Suzuki et al. 1998).
According to the authors, those compounds are less likely to form covalent bonds;
therefore they should not be responsible for adhesion. The cleavage of the aromatic
nuclei of lignin was also reported at high severity, where the mechanical properties of
molded products are decreasing. Lignin modifications due to steam pretreatment were
confirmed by use of FTIR and NMR analyses (Laemsak and Okuma 2000; Suzuki et al.
1998).
Contradictorily, Klason lignin has been sometimes reported to decrease slightly
with severity of steam pretreatment, while organic soluble components (soluble lignin)
increased (Anglès et al. 1999). This fact was supported by steam injection experiments,
as Klason lignin was reported to be degraded proportionally to steam pressure and time of
steam pressing, while the relative composition in acid soluble lignin increased (Widyorini
et al. 2005b). As far as hot pressing is concerned, degradation of lignin has been reported
to increase with temperature, showing an increasing methanol yield (Okuda et al. 2006b).
In this same paper, FTIR measurements showed cleavages of lignin intermonomer
linkages during hot pressing, demonstrating the degradation of some parts of lignin,
which were thus more extractible with methanol and did not appear in the residue. This
shows that these molecules did not create covalent bonds; they might nonetheless be
plasticizers for lignin (Bouajila et al. 2005).
According to Widyorini et al. (2005c) the syringyl / guaiacyl (S/G) ratio
decreased with severity of steam treatment, whereas in hot pressing conditions (without
steam), the S/G ratio remained similar to the starting material. This showed that steam
treatment degraded syringyl groups more than hot pressing. They also reported that the
cinnamic acid / guaiacyl ratio (C/G) decreased with increasing severity of treatment and
was well correlated to the strength of the composites. Tanahashi et al. (1990) proposed a
complete degradation mechanism of lignin during steam explosion by treating extracted
lignins, but the methodology remained unclear and no explicit conclusions were drawn.
Okuda et al. (2006a, 2006b), observed that the benzaldehyde yield of extraction
decreased during hot pressing, showing that some lignin residues experienced
condensation reactions. The authors claimed that guaiacyl acid could be the favorite

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molecule for condensation reactions. FTIR showed that new compounds were created,
which confirmed reactions on lignin. However the crosslinking was not demonstrated in
the cited work, and the authors mentioned that the condensation may occur to form small
molecules instead of a real network necessary to obtain a matrix effect and thus explain
the better bonding properties. Cristescu and Karlsson (2013) reported recently that beta
ether and methoxyl groups subjected to condensation reactions corresponded to good
adhesion properties and water resistance.
According to Ito et al. (1998a) the lignin content changes were not correlated to
the water resistance of the square compressed wood logs materials. According to the
authors, the mechanism of shape fixation against water relied more on cellulose
crystallization than on lignin. Except for rare reports like the previous one, the hypothesis
according to which lignin is important for selfbonding and strength of molded products is
vastly supported (Mason 1928; Howard and Sandborn 1937; Suzuki et al. 1998; Bouajila
et al. 2005; Imanishi et al. 2005; Okuda et al. 2006b; Yamashita et al. 2007). For
instance, the addition of methanol extractives in fibers prior to molding increases the IB,
while the material from which they have been extracted had a lower IB (Fig. 11) (Okuda
et al. 2006a). In this example, kenaf core powder with an average particle size of 53 µm
was used and pressed into 0.8 g/cm3 density binderless boards. The water properties also
decreased with removal of those extractives, and improved upon addition. The addition of
periodate lignin also enhanced the IB, while adding extracted holocellulose (therefore
"diluting" lignin) led to its decrease (Okuda et al. 2006a).

Fig. 11. Experiment of methanol extractives (lignin components) addition (E-type) and removal
(R-type) compared to original kenaf core powder (republished from Okuda et al. 2006a, with kind
permission of the Japan Wood Research Society).

Lignin softening and “activation”

As mentioned by van Dam et al. (2004b) based on literature reports, steam
explosion lignin and organosolv lignins are very reactive and can be used as adhesives for
particleboards. They could replace up to 50% of synthetic binders (phenol / phenolic
based resins, based on which an uncountable number of patents have been published),
although the effective use for it remains uncertain on a industrial scale (Gosselink et al.
2011). The endotherm at 140 °C that disappeared on a second heating was attributed by
some authors to the softening of lignin, during which they believed irreversible
condensation (dehydration + crosslinking) happened (van Dam et al. 2004b). Recent
work on thermal analysis of lignin seems to attribute this first endothermic event around
150 °C to the fusion of lignin. Some other high endothermic peaks above 180 °C were
associated with physical or/and chemical changes of lignin but are difficult to explain

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completely because of the structural complexity of lignin (Murugan et al. 2008; Kim et
al. 2014). This irreversible change in lignin occurring after being heated over a certain
temperature (180 °C) would possibly be related to the “lignin activation” phenomenon
previously reported (Mobarak et al. 1982). Activation is a term inherited from chemical
(oxidant and/or alkali) wood treatments that would involve the partial depolymerisation
(modification of active sites) to obtain new linkage capability. Activated lignin would
have a reduced melting point, and capacity to "polycondensate".
The effects of crossing the Tg value (softening point) by adjusting moisture and
temperature have tremendous potential in increasing board properties. Bouajila et al.
(2005) extensively studied the evolution of Tg of lignin in samples during hot pressing
and reported that the mechanical properties mostly depend on the possibility for the
molding temperature to exceed the Tg of lignin according to the local moisture in the
material. Such experiments that are classical in the industry of wood-based panels with
adhesive have been too rarely applied to binderless board production.

Mechanisms of Cohesion
In the industry of wood based panels, "adhesion" refers to the cohesive interaction
between fibers and the adhesive, "bonding" refers to interactions within the adhesive, and
"cohesion" is the sum of bonding and adhesion. In the case of hardboard, fibers/fibers
cohesion only is responsible for the cohesion. In the case of binderless boards, the sum of
fiber/fiber adhesion and in-situ matrix adhesion and bonding is responsible for the
cohesion and the science behind is still unclear compared to the classical wood-based
panels technology. These differences appear to be important:
 Plant materials have specific compositions, organization, and morphology that
influence the molded objects properties in a much wider variety than wood.
 Processing is generally made at higher temperatures for a longer time; thus many
chemical reactions are possible: hydrolysis, degradation, oxidation, and
recombination. These chemical changes that are undesirable in classical wood
panels processing are in binderless necessary preconditions for self-bonding.
 Compression of wood particles in the case of wood-based panels with adhesive is
necessary, but pressure is an even more crucial parameter in the case of binderless
boards processing: densities vary in a wide (mostly higher density) range although
the density of wood based panels is calibrated (0.6 to 0.7 g/cm3 for particleboards,
0.65 to 0.85 g/cm3 for fiberboards).
 In the classical wood panels industry, processing (i.e. pressing) is adjusting
pressure time and temperature to evaporate excess of water and cure the resin. In
the case of binderless molding, processing must be adjusted in order to trigger the
bonding wherein all main parameters are interdependent: for example
composition and structure of starting material will determine equilibrium moisture
content, which will be determinant on the physico-chemical properties of fibers
(glass transition temperature, flow ability, crystallinity) but also on the
mechanisms of degradation of lignocellulosics components, and all this will be
impacted by processing parameters especially time and temperature.
The comprehensive understanding of the exact mechanisms that would fully explain the
properties of binderless plant materials is difficult, but there are some concepts and ideas
that can help to improve their properties. There are some parallels to make between

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selfbonded plant materials and wood welding on the one hand, and thermal wood
treatment in the other hand:

Glass transition of cell-wall polymers

The importance of glass transition in wood-based materials inherited from the
polymer science and was extended to biopolymers in the early work of Slade and Levine
(Slade and Levine 1991). All polymers undergo a transition from a glassy state to a
rubbery state at a specific temperature, which is extremely dependent on their moisture
content (Fig. 12).
In the rubbery state, polymers acquire enough molecular motion to deform. They
adapt to the mechanical constraints, which increases surface contact and creates a matrix
effect inside the composite. Depending on their molecular structure and hygroscopicity
(depending on the polar character of the polymer), the glass transition temperature (Tg)
varies from around 200 °C in the dry state to around 0 °C for 20% MC for most
carbohydrates. The Tg's of wood polymers in the dry state are reported to be 220 °C
(cellulose), 170 °C (hemicellulose), and 200 °C (lignin) (Back 1987). An illustration of
the Tg-moisture dependence is the possible molding of hardboard in wet process without
using binders although binders are necessary in the dry state because core layer cannot
reach the Tg of wood polymers.

Fig. 12. Glass transition temperature of biopolymers according to their water content (adapted
from Gaudin et al. 1999; Micard et al. 2000; Slade and Levine 1991)

Yet, although isolated lignin and hemicelluloses are amorphous and exhibit glass
transitions, their behavior inside the organized cell-wall structure is not as obvious (Irvine
1985), and it becomes even more complicated when they are partially or completely
degraded into low molecular weight compounds, for which no thermoplastic effect could
be reasonably taken into account. In many cases, the effect related to the glass transition
depends on raw material structure, mechanical, chemical, and enzymatic pre-treatments
(Álvarez et al. 2011), as all these effects influence molar mass and molar mass
distribution of the material as well as secondary forces additionally responsible for the
integrity of the material. Nevertheless, the presence of lignin, free enough to show a
relaxation peak when tested in DMA, is determinant to improve mechanical properties
(Bouajila et al. 2005). The compression process on lignocellulosic fibers at a temperature
above lignin glass transition temperature (which can go above 150 °C when water is

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evaporated) gave the best properties. A parallel can be made with thermomechanical
refining of wood that requires to place the fibers in moisture / temperature conditions
above the Tg's of polymers (hemicelluloses, amorphous part of cellulose, lignin) in order
to separate the fibers along the tangential orientation of other fiber direction and obtain
higher surface development (Irvine 1985).
The thermoplastic behavior of biopolymers from plant cells have also been
described for fibrous raffinate of sunflower containing residual proteins (Evon et al.
2010) and on wheat straw for the production of pellet by dry extrusion (Stelte et al.
2011).
Similar conclusions have been reported concerning the cohesion obtained by
wood friction welding. Temperatures around 200 °C are reached in the glue line, which is
densified, and the thermoplastic effects of lignin and hemicelluloses are predominant
(Gfeller et al. 2003).

Cross-linking of lignin-carbohydrate-complex (LCC)

In the field of wood treatment in order to increase its durability many research
works have attempted to explain the mechanisms of chemical changes during a thermal
treatment depending on the operating conditions. Factors considered have included the
presence or not of oxygen or of water vapor, temperature, and time. These processes
involve then clearly the same kinds of modifications as hot-pressing or wood welding.
Some of these findings are similar to those discussed in the previous part on the
heat-induced degradation of lignocellulosic components: a reduction of free hydroxyl
groups through the degradation of hemicelluloses (Srinivas and Pandey 2012; Singh et al.
2013; Liu et al. 2014), a decrease of cellulose content, like determined on bamboo
samples (Zhang et al. 2013), a change on lignin structure with an increase of the
aromaticity (Park et al. 2013), but also some physical effects such as a decrease of nano-
pore shares and fiber saturation point (Zauer et al. 2014).
The increase of durability of heat-treated wood (two stages, first in excess of
water vapor then in a dry state under an inert atmosphere, temperature below 200 °C) is
mainly induced by cross-linking mechanism (Boonstra and Tjeerdsma 2006; Tjeerdsma
et al. 1998). First the hemicelluloses are degraded, producing acids that further increase
the depolymerization rate of carbohydrates (of the remaining hemicelluloses and the
amorphous cellulose); then lignin is cleaved and activated with an increase of free
reactive sites. In a second step, the cross-linking of the lignin network occurs, involving
some products of hemicelluloses degradation such as furfural or methyl-furfural, which
was confirmed in binderless particleboard production (Cristescu and Karlsson 2013;
Lamaming et al. 2013). Polycondensation reactions are not completely elucidated but are
thought to be responsible for the lignin content increase after heat treatment and
obviously related to the improvement of water resistance.

Hydrogen bonding and co-crystallisation of cellulose as a consolidation mechanism

The most admitted hypothesis in binderless board production is that cellulose does
not play an important role in bonding (Anglès et al. 2001). But, looking at the results
obtained by hot pressing of pure cellulose, there might be a possibility of pressure-driven
selfbonding in cellulose, as some mechanical properties obtained by direct compression
at high pressure of cellulose powder have been reported (e.g. Pintiaux et al. 2013). The
mechanisms of cohesion are thought to rely on fibril aggregation through hydrogen
bonding (Nilsson et al. 2010) or other interactions, which has been recently debated

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(Glasser et al. 2012). Crystallinity changes were also observed (Vaca-Medina et al.
2013), which could confirm the importance of co-crystallization mechanisms (Newman
2004).

CONCLUSION AND FUTURE DIRECTIONS

Production of binderless material by thermo-compression of lignocellulosic fibers

is a very simple technique in front of a very complicated science: it requires studying
many concomitant phenomena involving the disorganization and re-organization of
complicated multi-components of biological structures. Most of the time, research studies
on binderless boards do not take advantage of the classical phenomena that have been
vastly investigated in the thermocompression of industrial wood-based panels with
adhesive. In many studies, it is clear that the bridge between these two different worlds of
science has not been crossed. Lots of improvements for this new kind of materials are
still possible, and although the complete understanding of the occurring transformations
remains unachieved to date, some elements that have been highlighted in this review will
help to guide researchers who would like to study these fascinating transformations and
improve future materials.
From the analysis of the literature, it appeared that correct mechanical properties
can be obtained without pretreatment (i.e. particleboards type) in the case of certain raw
materials, but when steam treatment is involved it seems that any lignocellulosic material
would be moldable (i.e. in fiberboards type) and would result in suitable mechanical
properties. Water resistance, however, remains low and does not match the standards on
industrial wood-based panels. Regarding the choice of raw materials, the use of by-
products is preferred and the presence of lignin (and eventually of storage biopolymers
even in small quantities) is definitively favorable. Mixing plants together and structural
associations (layers etc.) have been barely studied and could be of great interest.
The eco-friendly argument is very often offered as a competitive feature of such
materials, but looking more precisely at the energy cost of such processing is necessary to
qualify its eco-compatibility. There is a lot of room for Life Cycle Analysis of this kind
of materials and processes, which should produce interesting and innovative studies.
Temperature of molding is undoubtedly the most important processing parameter
for which the limiting factor is delamination. High temperatures are favorable to improve
water-resistant properties and are responsible for the skin-effect and "plastic" touch. A
minimum of moisture is necessary in order to obtain satisfactory mechanical properties,
but this minimum value and the effect of higher moisture are still unclear. During
compression at elevated temperature, steam is generated from the initial moisture, and
effects can be compared to changes occurring during steam pretreatments. Some
technological tricks can be applied to prevent delamination, but more research is needed
in order to better understand the relation between moisture / temperature and
delamination, because molding conditions that give the best properties are very close to
those triggering delamination.
Steam treatment involves a combination of defibration, degradation (of
hemicelluloses and part of lignin mainly), and lignin modifications (plasticization i.e.
decrease of Tg, partial depolymerization, flowability, and condensation to a lower extent).
Moderate severity of steam treatments generally provides the best bending properties.
The highest severity of steam treatment was reported to increase water resistance and IB:

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these two parameters seem to be correlated, which could be further studied. In our
opinion, a moderate severity of pretreatment in one hand and a higher severity in the
other hand would favor two different mechanisms, that we named "thermoplastic" and
"thermoset", respectively. These two main bonding mechanisms would happen in thermal
treatment and any kind of thermocompressive molding of natural fibers, even at moderate
pressure, which is not the case of the quite unknown co-crystallization phenomenon
reported on high pressure molding of pure cellulose; and for this reason, is considered
apart.
Thus, it makes sense to think in terms of a "thermoplastic" mechanism, which
would mostly occur under mild conditions of processing (temperatures below 160 to
180 °C), during which the glass transition temperature of lignin and hemicelluloses (and
also starch and proteins if concerned) is passed. In the resulting rubbery state, polymers
would deform, filling the voids in and between particles, and giving the highest
mechanical properties (MOR, MOE). The "thermoplastic" mechanism can be expected to
occur more easily if polymers are freed up by chemo-mechanical destructuration and
plasticization brought about by pretreatments because of the highly organized native state
in the plant’s cell wall.
Secondly, one can envision a "thermoset" mechanism, which involves chemical
reactions at higher temperature (over 200 °C), with more important depolymerization /
degradation of the polymers, leading to the production of weak acids and contributing to
even more degradation by autohydrolysis. Highly reactive degradation products,
especially aldehydes (particularly furfural and hydroxymethyl furfural), would participate
(together with lignin) in the creation of new compounds (e.g. lignin-cellulose complexes)
and in the cross-linking of the composite matrix, which brings about bonding between the
cellulosic particles and gives rise to water-resistant properties.
Because of the gradients (density / moisture / temperature) occurring within the
processed material, depending on product shape (e.g. thickness), temperature, moisture
and time have to be adjusted together to control the thermoplastic/thermoset balance.
Lignin for instance, which is reported to be the most important polymer for the
development of bonding in the absence of an added adhesive, would have different
behaviors: in the "thermoplastic" mechanisms lignin would be "activated", plasticized,
and experience flow and some degradation, whereas in the "thermoset" mechanisms,
condensation reactions would result in complexes with the other polymers. The
"thermoplastic" / "thermoset" limit, however, remains unclear also because it is extremely
complicated to study lignin itself, as extracted lignin is always degraded and would not
behave as native lignin (as it is inside the cell wall).
Surely, the "thermoplastic" and "thermoset" mechanisms coexist, and no limit can
be precisely set. Yet, delamination is thought to occur at the transition from
"thermoplastic" to "thermoset". This is because of the loss of native structure due to
thermoplastic flow and disorganization of the cell wall structure and the release of
volatile compounds and water. At the same time more polymer/polymer interactions take
place during the compression in the rubbery state, and these involve organic compounds
produced in the course of thermal degradation. When the "thermoset" mechanism is
predominant, water would be consumed by hydrolysis and volatile compounds would be
condensed into bigger non-volatile structures. Much further work is needed toward the
understanding of these physico-chemical reactions for these simple but elegant materials
to find a real industrial market.

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ACKNOWLEDGMENTS

The authors would like to thank the ANR (French National Research Agency), the ANRT
(French National Research and Technology Agency), and The Green Factory (business
partner) for their financial support.

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Article submitted: August 4, 2014; Peer review completed: September 5, 2014; Revised
version received: December 5, 2014; Accepted: December 11, 2014; Published: January
16, 2015.

Pintiaux et al. (2015). “Thermo-pressed biomass,” BioResources 10(1), 1915-1963. 1963