2 Phenol
Formaldehydes
A. Pizzi and C.C. Ibeh
LERMAB, University of Lorraine, Epinal, France and King Abdulaziz University, Jeddah, Saudi Arabia
O U T L I N E
Introduction
Raw Materials
Phenol
Introduction
A number of different thermosetting adhesives
and resins are used industrially. Among these, ther-
mosetting resins based on the use of formaldehyde-
based resins obtained by polycondensation have
dominated the field for many decades. Many of
these are used mainly for their application to wood
and wood fiber panel products of all types and for
a variety of other major applications.
Formaldehyde-based thermosetting resins constitute
well more than 50% by volume (NB: not by value) of
all the adhesives used today in all fields. Thus, resins
such as urea-formaldehyde (UF), phenol-formaldehyde
(PF), melamine-formaldehyde (MF), melamine-urea-
formaldehyde (MUF), resorcinol-formaldehyde, and
other minor ones constitute today, with some
notable exceptions, a low margin commodity produced
in great quantities. The reason for such wide use is
mainly their relative ease of manufacture and the rela-
tively low plant investment necessary to produce such
resins. This apparent ease belies the high technology
that is in-built in such resins, newcomers to this field
being easily deceived by the apparent simplicity of their
chemistry and of their preparation. While their basic
chemistry and technology is quite understandable, the
development of applicable formulations acceptable to
today’s sophisticated markets is not an easy matter.
In the form in which they are delivered, these
adhesive resins are mainly liquid and consist of
mainly linear or branched oligomeric and polymeric
molecules in an aqueous solution; they are also partly
Handbook of Thermoset Plastics. DOI: http://dx.doi.org/10.1016/B978-1-4557-3107-7.00002-6
© 2014 Elsevier Inc. All rights reserved.
13 Resinification (Production) of
Phenol
Formaldehyde Resins 16
15
Phenolic Resins in Friction Materials 29
15
References 41
a dispersion of molecules in these same aqueous solu-
tions. During hardening and gelling they convert irre-
versibly into insoluble and non-melting three-
dimensionally cross-linked networks. The hardening
conditions used can be acidic (for aminoplastic resins
such as those based on urea and melamine), highly
alkaline or acid (phenolic resins), or neutral to light
alkaline (resorcinol resins, tannins).
The consumption of resins for thermosetting
formaldehyde-based wood adhesives has by far the
greatest market volume in North America and
Europe (1997 and 1999, respectively), based on
resin solids (Table 2.1).
Other than their main application as wood panel
adhesives, other major fields of application for these
adhesives are as foundry cores and mold binders,
and for the impregnation and bonding of paper with
PF and MF resins to obtain resistant laminates.
There are applications of these resins other than as
adhesives, such as in preparation of rigid foams, as
binders for temperature-resistance fibers for break-
lining, and many others. The total worldwide pro-
duction and consumption of urea-formaldehyde (UF)
resins and phenolic (PF) resins for all uses is not
exactly known, but is today reputed to be approxi-
mately 10
11 million tons/year for UF resin solids
and 3.5
4 million tons for PF resin solids.
Form a purely technical point of view, these resins
have evolved during the last few decades to yield:
• Highly reactive adhesives with quick gelling
and hardening behavior and steep increases in
13
14
Table 2.1 Estimated Consumption of Wood Adhesive Resin Solids in North America and
Western Europe
Polymer type North America
kTons
Urea-formaldehyde (UF) 960
Melamine-urea-formaldehyde (MUF)
350
Phenol-formaldehyde (PF) 567
Resorcinols (PRF) 12

1997

1999
bonding strength even at a low degree of
chemical curing.
• Highly reactive adhesive mixes by inclusion of
additives such as accelerators, special hard-
eners, cross-linkers, and others.
• Lower cost resins that maintain the same
peformance, or even improve it.
• More environmentally acceptable adhesives.
Thus, the minimization of the content in expen-
sive melamine in exterior-grade MUF-resin, the
marked decrease of the content in expensive resor-
cinol in structural exterior-grade PRF adhesives, or
the development of some fast-curing alkaline PF
resols are glaring examples of these trends.
The impact of resins on various environmental
aspects such as waste water and effluents and emis-
sion of noxious volatile chemicals (e.g. formalde-
hyde during the production of, and from, finished
boards) has been an important trend in the last cou-
ple of decades, and promises to have future impor-
tance. The emission of formaldehyde was a matter
of concern in the past, a problem that has now been
solved. Also of concern are the effluent discharges
of free phenols or other monomers.
Phenolic Resins
Phenol-formaldehyde resins (phenolic resins, PF),
the first thermosetting plastics, are considered to
be the first truly synthetic commercially available
plastic resins. Unlike celluloids, the first man-
made plastic resins, phenolic resins are made from
purely synthetic materials. Today resins based on
HANDBOOK OF THERMOSET PLASTICS
Western Europe Total
kTons kTons
2600 3560
350
260 827
6 18
natural polyphenolic materials are starting to be
used industrially, namely condensed tannin resins.
Phenol-formaldehyde resins are formed by the
chemical reaction between phenols and formalde-
hyde solutions (formalin).
Work in the area of phenols and formaldehydes
began prior to the 20th century with Adolf Bayer [1]
in 1872 and Losekam [2] in 1889. The first commer-
cially available phenolic resin, called Laccain, was
introduced by Blumer [2] in 1902 as a substitute for
shellac; it was not a commercial success [3]. The use
of phenolic resins was popularized by the “heat and
pressure” patents [3
6] of Dr. Leo H. Baekeland in
1907; hence, he is known as the “father of phenolic
resins.” Today, some of the most popular phenolic
resins bear the trade name “Bakelite” in reference to
the company (General Bake-lite Company) he
formed in 1910. Bakelite Corporation became a sub-
sidiary of Union Carbide [3] in 1939.
Baekeland’s patents involved the use of:
1. High pressure and a closed mold to overcome
the problems of bubble formation and the
evolution of gases and steam.
2. Fillers, such as wood flour, to overcome the
problem of the brittleness of cured phenolic
resin.
These inventions made it possible, using phenol-
formaldehyde resins, to cost effectively produce
molded parts. Prior to Baekeland’s inventions, it
was necessary to use low-temperature processing
methods to suppress the evolution of steam and
gases. These methods caused bubble formation and
expensive, long production cycles. Also, the use of
2: PHENOL
FORMALDEHYDES 15

fillers enhances properties and lowers the cost of Cumene Process for Making
cured resin.
Phenol
Over the years, phenolic resins have competed
favorably with newer plastic resins. In 1993, In the cumene process, commercialized in 1952
phenol-formaldehyde resins had a consumption by H. Hook, the reaction between benzene and pro-
volume of 3.07 billion pounds, ranking second only pylene with an aluminum chloride catalyst yields
to polyurethane (3.476 billion pounds) among ther- isopropyl benzene (cumene). Cumene oxidizes to
mosets. In 1983, the American Chemical Society hydroperoxide, which is broken down by acidifica-
organized a symposium [7] entitled “Phenolics tion into phenol and acetone:
Revisited, 75 Years Later” in Washington to show-
AlCl3
case the importance of phenolic resins. Today, phe- C6 H6 1 CH2 5 CHCH3 - C6 H5 CHðCH3 Þ2
nolics are used in many areas, such as insulation, benzene propylene catalyst cumene
electrical devices, automotive parts, and adhesives. O2
C6 H5 CHðCH3 Þ2 - C6 H5 COOH
cumene cumene
hydroperoxide

Raw Materials
Phenol-formaldehyde resins are general-purpose
thermosets formed mainly by the polycondensation
reaction between phenols and formaldehyde solu-
tions. The three major raw materials for making
phenolic resins are:
1. Phenol C6H5OH.
2. Formaldehyde CH2O.
3. Hexamethylene Tetramine (CH2)6N4.
acid
- C6 H5 OH 1 CH3 COCH3
Phenol Acetone
Raschig Process
The Raschig process passes benzene, hydrogen,
and air over a heated copper catalyst at 200°C to
300°C. The intermediate product is chlorobenzene
and water in the gaseous state. The water hydro-
lyzes the chlorobenzene, when passed over hot sil-
ica catalyst at 500°C, to phenol and HCl.

1 Cu=Fe
Other phenols, such as cresols (monomethyl- C6 H6 1 HCl 1 O2 - C6 H5 Cl 1 H2 O
phenols), xylenols (dimethyl-phenols), resorcinol benzene 2 catalyst1 chloro- water
hydrogen-chloride 200°2300°C benzene
(m-dihydroxybenzene), and alkylated-phenols, can
be used in place of phenol, but their usage is lim- SiO2
C6 H5 Cl 1 H2 O - C6 H2 OH 1 HCl
ited due to the availability of less expensive syn- chloro- water catalyst1 phenol hydrogen
thetic phenol. Resorcinol-based resin can be room- benzene 500°C chloride
temperature cured and used in laminated beams for
churches, boat keels, etc. Alkylated phenols, such
as p-tertiary butyl phenol and p-tertiary octyl phe- Dow Process
nol, are used, respectively, as tackifiers in pressure
The Dow process, established in 1920, uses the
sensitive tapes and automobile tires.
direct vigorous reaction of chlorobenzene and
sodium hydroxide solution at 300°C and 4000 psi:

300°C
Phenol C6 H5 Cl 1 NaOH - C6 H5 OH 1 NaCl
chloro sodium 4000 psi phenol sodium
benzene hydroxide chloride
Phenol is primarily obtained from the fractional
distillation of coal tar and various synthetic pro-
cesses. There are at least six known commercial
synthetic processes for making phenol of which the
four most common are Cumene, Raschig, Dow, and Formaldehyde (CH2O)
Sulfonation. The Sulfonalion process, although Formaldehyde is produced by the controlled
popular at one time, is no longer in use. catalytic oxidation of methyl alcohol (methanol).
16
The result is the dehydrogenation of methanol to
formaldehyde. In the process, a mixture of metha-
nol vapor and air is passed over a heated copper
oxide catalyst at 300°C to 600°C to produce a mix-
ture of formaldehyde and water. The product is a
37% solution of formaldehyde that is subsequently
enriched to a 40% solution known as formalin:
1 300°2600°C
CH3 OH 1 O2 - HCHO 1 H2 O
methanol 2 CuO formaldehyde
Impurities in formalin include formic acid as a
side product and residual methanol. The residual
methanol serves as a stabilizer during storage,
whereas the formic acid is removed. This process
was commercialized as the die Formox process in
the late 1950s by the Rcichhold Chemical, Inc.
Hexamethylene Tetramine
(Hexamine or “HEXA”) (CH2)6N4
HEXA is produced by passing ammonia gas into
a 30% formaldehyde solution at room temperature:
6CH2 O 1 4NH3 - ðCH2 Þ6 N4 1 6H2 O
formaldehyde ammonia HEXA
Resinification (Production)
of Phenol
Formaldehyde Resins
Reaction Chemistry
The reaction mechanism between phenol and
formaldehyde is not yet completely known. It is
known, however, that the reaction is initiated by
the activation of the benzene ring by the hydroxyl
group such that a methylol group (CH2OH) joins
the benzene nucleus at the ortho- and para-
positions. The reaction produces a resole if an alka-
line catalyst is used and a novolac if an acid
catalyst is used.
From the work of Baekeland and Lebach [2],
three basic stages are recognized in the phenol-
formaldehyde reaction:
1. A-stage or resole.
2. B-stage or resitol.
3. C-stage or resite.
HANDBOOK OF THERMOSET PLASTICS
At the A-stage, the initial condensation products
are mainly alcohols. The resin at this point is ther-
moplastic and soluble in inorganic solvents. At the
B-stage, there is a higher degree of condensation
and some cross-linking, with a consequent increase
in molecular weight and viscosity, and a decrease
in solubility. The resin is not fully cured; it is soft
and fusible when hot, but hard and brittle when
cold. At the C-stage, the degree of polymerization
water and cross-linking is very high, and there is almost a
complete cure. The resin is infusible and insoluble.
Polymerization Process
Phenols condense initially with formaldehyde in
the presence of either acid or alkali to form a
methylolphenol or phenolic alcohol, and then
dimethylolphenol. The initial attack may be at the
2-, 4-, or 6-position. The second stage of the reac-
tion involves methylol groups with other available
phenol or methylolphenol, leading first to the for-
mation of linear polymers [8], and then to the for-
mation of hard-cured, highly branched structures.
Novolak resins are obtained with acid catalysis,
and with a deficiency of formaldehyde. A novolak
resin has no reactive methylol groups in its mole-
water vapor
cules and therefore without hardening agents is
incapable of condensing with other novolak mole-
cules on heating. To complete resinification, further
formaldehyde is added to cross-link the novolak
resin. Phenolic rings are considerably less active as
nucleophilic centers at an acid pH due to hydroxyl
and ring protonation (Scheme 2.1).
However, the aldehyde is activated by proton-
ation, which compensates for this reduction in
potential reactivity. The protonated aldehyde is a
more effective electrophile (Scheme 2.2).
•• •+• +OH
H OH
••
OH
••
H+
+
H H
Scheme 2.1
H H + H +
C O + H+ C OH C OH
H H H
Scheme 2.2
2: PHENOL
FORMALDEHYDES 17

The substitution reaction proceeds slowly and
condensation follows as a result of further proton-
ation and the creation of a benzylcarbonium ion
that acts as a nucleophile (Scheme 2.3).
Resols are obtained as a result of akaline catalysis
and an excess of formaldehyde (Scheme 2.4). A resol
molecule contains reactive methylol groups. Heating
causes the reactive resol molecules to condense to
form large molecules, without the addition of a hard-
ener. The function of phenols as nucleophiles is
strengthened by ionization of the phenol, without
affecting the activity of the aldehyde.
A carbonium ion mechanism is, however, more
likely to occur for reaction II, although strong evi-
dence for a quinone methide mechanism also exists
[9
11]. Megson [9] also states that phenolic nuclei
can be linked not only by simple methylene bridges
but also by methylene ether bridges. The latter gen-
erally revert to methylol bridges if heated during
curing, with the elimination of formaldehyde.

+ OH
+O OH
H
H CH2OH
H +
•• – CH2OH CH2OH

H+

+ OH
OH OH OH OH
+ +
CH2 H H2C CH2 OH
•• – H

Scheme 2.3

OH O O O O
H H
•• ••
+ OH
-
••

O O
Ο
H H
+ δ −δ CH2 ΟΗ
•• CH2OH
H2C O

OH
CH2

OH OH
CH 2OH
QUINONE
METHIDE

OH OH OH OH
CH2 CH2 CH2OH

Scheme 2.4
18
OH OH
O
CH2
••
H The solid resols average three to four phenolic
OH
CH2
OH OH
OH
CH 2OH CH2 CH2OH
Scheme 2.5
The difference between acid-catalyzed and base-
catalyzed processes is (1) in the rate of aldehyde
attack on the phenol, (2) in the subsequent conden-
sation of the phenolic alcohols, and to some extent
(3) in the nature of the condensation reaction. With
acid catalysis, phenolic alcohol formation is rela-
tively slow (Scheme 2.5). Therefore, this is the step
that determines the rate of the total reaction. The
condensation of phenolic alcohols and phenols
forming compounds of the dihydroxydiphenyl-
methane type is rapid.
The latter are therefore predominant intermedi-
ates in novolak resins (Scheme 2.5).
Novolaks are mixtures of isomeric polynuclear
phenols of various chain lengths with an average of
five to six phenolic nuclei per molecule. They con-
tain no reactive methylol groups (Scheme 2.5) and
consequently cross-link and harden to form infus-
ible and insoluble resins only when mixed with
compounds that can release formaldehyde and form
methylene bridges (such as paraformaldehyde or
hexamethylenetetramine).
In the condensation of phenols and formaldehyde
using basic catalysts, the initial substitution reaction
(i.e. the formaldehyde attack on the phenol) is faster
than the subsequent condensation reaction.
Consequently, phenolic alcohols are initially the pre-
dominant intermediate compounds (Scheme 2.5).
These phenolic alcohols, which contain reactive
methylol groups, condense either with other methylol
groups to form ether links, or more commonly, with
reactive positions in the phenolic ring (ortho or para
to the hydroxyl group) to form methylene bridges
(Scheme 2.5). In both cases water is eliminated.
Mildly condensed liquid resols, the more impor-
tant of the two types of phenolic resins in the
HANDBOOK OF THERMOSET PLASTICS
formulation of wood adhesives, have an average of
fewer than two phenolic nuclei in the molecule.
nuclei but with a wider distribution of molecular
size. Small amounts of simple phenol, phenolic
alcohols, formaldehyde, and water are also present
in resols. Heating or acidification of these resins
causes cross-linking through uncondensed phenolic
alcohol groups (Scheme 2.5), and possibly also
through reaction of formaldehyde liberated by the
breakdown of the ether links.
As with novolaks, the methylolphenols formed
condense with more phenols to form methylene-
bridged polyphenols. The latter, however, quickly
react in an alkaline system with more formaldehyde
to produce methylol derivatives of the polyphenols.
In addition to this method of growth in molecular
size, methylol groups may interact with one
another, liberating water and forming dimethylene-
ether links(aCH2-O-CH2a). This is particularly
evident if the ratio of formaldehyde to phenol is
high. The average molecular weight of the resins
obtained by acid condensation of phenol and form-
aldehyde decreases hyperbolically from over 1000
to 200, with increases in the molar ratio of phenol
to formaldehyde from 1.25:1 to 10:1.
Usually alkaline NaOH is used as catalyst in an
amount up to one mole per mole phenol (molar ratio
NaOH/P), which corresponds to a portion of alkali
in the liquid resin of approx. 10 mass%. The pH of a
phenolic resin is in the range 10
13. The biggest
part of the alkali is free NaOH, a smaller part is
present as sodium phenate. The alkali is necessary
to keep the resin water soluble via the phenate ion
formation in order to achieve a degree of condensa-
tion as high as possible at a viscosity that still can
be used in practice. Additionally, the alkali signifi-
cantly drops the viscosity of the reaction mix.
Hence the higher the alkali content, the higher the
possible degree of condensation of the resin; hence
the higher is the hardening reactivity of the resin
and therefore the shorter the necessary curing time.
Higher alkali content, however, also has some
important disadvantages. The equilibrium moisture
content in humid climates increases with the alkali
content as well as some hygroscopic (longitudinal sta-
bility, thickness swelling, water absorption) and
mechanical properties (creep behavior) become worse.
Besides NaOH other basic catalysts can also be
used, like Ba(OH)2, LiOH, Na2CO3, ammonia or
hexamine, some of these being commercially used
2: PHENOL
FORMALDEHYDES 19

and others not. The type of catalyst significantly Water Out Vent
determines the properties of the resins [12,13]. Condenser
Decreasing the proportion of alkali in PF-bonded
products yields some advantages. Ammonia evapo-
rates as a gas during the hot curing and therefore To
Vacuum
does not contribute to the alkaline behavior and the Reactants
pump
hygroscopicity of the products. In wood panels Motor
Pressure
Water in
applications it is important to hold the pH fairly guage
high as long as possible during hot pressing in
order to guarantee an high reactivity and hence a Safety
short curing or pressing time [14,15]. valve
Still Distillate
The penetration behavior and the “grip“ of the Steam tank
Water
adhesive onto the substrate depends strongly on the
molar mass of the resin: the higher the molar mass Stirrer
Out
(more or less equivalent to the viscosity of the resin
at the same solid content), the worse its wetting
capacity and the lower its penetration into the sub- Steam
strate surface [16,17]. Lower molar mass chains are jacket
responsible for good surface wetting, however, too Condensate
low a molar mass can cause over-penetration and
Discharge valve Temperature
hence starved glue lines [18]. indicator

Resole Phenolic Resins
Resole phenolic resins are produced by polymer-
izing (heating) a 1:1 (or more) molar ratio of phe-
nol and formalin in a reactor vessel (Figure 2.1) in
the presence of an alkaline catalyst such as ammo-
nia, sodium carbonate, or sodium hydroxide at 100°
C for about 1 hour. It is usual to have 1.1 to 1.5
mole of the formaldehyde for each mole of phenol.
Polymerization is stopped short of the gel point
by cooling (B-staging). The product at this point is
an intermediate resole phenol-form-aldchyde resin.
If a solid product is desired, the intermediate is
dried by healing under a vacuum for 3 to 4 hours to
prevent heat hardening.
Resole phenol-formaldehyde resin is a water sol-
uble methylol (aCH2OH) bearing thermoplastic.
The curing process to the final thermoset material
can be initiated by just heating the resole in a mold
above its gel point. The resole resins formed have
reactive methylol and hydroxyl groups. When
heated, resoles form larger molecules with methy-
lene cross-links without the use or addition of a
curing agent. The phenol-formaldehyde resin resini-
fication reaction is a typical polycondensation reac-
tion since water is given off as a by-product.
Resole phenolic resins have a short shelf life:
less than 1 year (less than 60 days in most cases).
They are referred to as one-step phenolics because
Water in
Figure 2.1 Schematic of typical reactor vessel for
the bulk polymerization of phenol-formaldehyde
resins [8,9].
they do not require curing agents, only heat. Casting
resins, bonding resins, and resins for laminating
paper and wood are made in this way.
Novolak Phenol
Formaldehyde
Resins
The polymerization of phenol-formaldehyde
novolak resin is carried out in the presence of an
acid catalyst such as oxalic acid, sulfuric acid,
hydrochloric acid, formic acid, and aromatic sulfu-
ric acids. Sulfuric and oxalic acids are the two most
commonly used. The gel point of the cure is delib-
erately delayed by using a phenol-formaldehyde
feedstock that is deficient in formaldehyde. It is
customary to use a phenol-formaldehyde ratio of
1:0.8 in the first stage (pre-polymerization).
Polymerization is carried out by heating the mix-
ture for 2 to 4 hours at reflux, with water removal
at temperatures as high as 160°C (Figure 2.1). The
resultant low-molecular-weight molten intermediate
is cooled. The glassy material is carefully crushed
20
and blended with hexamethylene tetramine
(HEXA) (in powder form) to produce a molding
compound. The HEXA is the second part or hard-
ener; hence, the blended resins are referred to as
two-step resins or novolac phenolic resins.
Upon heating the novolac resins to about 165°C
in a mold, the HEXA decomposes to provide the
formaldehyde necessary for the final curing. The
addition of HEXA gives the resin a final working
phenol-formaldehyde molar ratio of 1:1.5. Novolac
phenolic resins have an infinite shelf life under nor-
mal storage conditions.
A schematic of a reactor vessel used for the typi-
cal bulk polymerization process in tire resinifica-
tion of phenol-formaldehyde resins is shown in
Figure 2.1. The steam jacket provides the tempera-
ture condition needed for the polycondensation
reaction of phenol and formalin. The condenser
facilitates the condensation and removal of water
vapor resulting from the phenol/formalin reaction.
The removal of water from the system enhances the
phenol/formalin reaction and causes formation of
more phenol-formaldehyde resin. If the water was
not removed, the formation of phenol-formaldehyde
resin would be suppressed.
Differences Between Resole
and Novolac Phenolic Resins
The differences between resole and novolac phe-
nolic resins are:
1. Resole phenolic resins are produced by using
alkaline catalysts, whereas novolac resins are
produced via acidic catalysts.
2. Resole phenolic resins are produced via B-
staging while novolac resins are made by pre-
polymerization.
3. Resole phenolic resins are methylol-bearing
resins while novolacs are non-methylol-bearing
resins.
4. Resoles typically have a shelf life of less than
1 year (less than 60 days), whereas novolacs
have an infinite shelf life.
5. Resoles split off water when they cure while
novolacs give off ammonia when they cure.
6. Novolac resins are twice more dimensionally
stable than resoles.
HANDBOOK OF THERMOSET PLASTICS
7. Resoles are typically casting and bonding
resins, whereas molding compounds are made
from novolacs. Of course, some molding
compounds can be made from resoles.
8. Resoles are usually liquids while novolacs
are solids.
Properties of Phenolic Resins
Phenolic resins are typically opaque and range
from pale amber and dark brown to black in color.
Of course, some resoles are light in color prior to
processing. The dark color of phenolic resins limits
their application to a narrower market niche.
Phenolic resins are available in flakes, films, and
liquid and powder forms.
Phenolic resins are considered to be general-
purpose thermosets though they can be com-
pounded into engineering structural materials. They
cost about $0.60 to $0.85 per pound [19
21]
depending on make and grade. Phenolics are the
second most used thermosets, with an annual con-
sumption volume of 3.07 billion pounds (in 1993).
Phenolic resins (and thermosets in general) are
brittle without fillers. It is customary to use fillers
and other additives to achieve their desired proper-
ties and characteristics. Hence, formulation is the
essence. Table 2.2 presents the typical properties of
different forms of phenolic resins, and Table 2.3
gives the parts per hundred (phr) resin composition
of different formulations for phenolic molding
resins. The effect of fillers on phenolic resin prop-
erties can be seen from the data in Table 2.2. For
example, the compressive strength of unfilled phe-
nolic molding resin is about 10,000 to 30,000 psi
compared to 26,000 to 70,000 psi for glass-filled
phenolic molding resins.
Phenolic resins exhibit a high degree of property
variance due to physical and chemical variation in
composition. To discuss the properties of the vari-
ous forms of phenolic resins based on their end
uses or processing forms such as casting, adhesives
and bonding, coating, laminating, and molding
resins would be cumbersome and virtually impossi-
ble. Although phenolic molding resins have only
about 6% of the phenolic resin market, they are
used in a wide spectnun of products that show the
essence of the properties and characteristics of
phenolics.
Table 2.2 Phenolic Resin Properties [11
14]

Casting Resin Molding Molding Resin Molding Resin Molding Resin

Properties Unfilled Resin Unfilled Cellulose Filled Woodflour Filled Glass Fiber Filled
Tensile strength (at break) 5,000
9,000 7,000
8,000 5,000
9,000 5,000
9,000 7,000
18,000
(psi)
Impact strength izod (notched) 0.24
0.4 0.2
0.36 0.2
0.6 0.24
0.6 0.5
18
(ft-lb/in.)
Compressive strength (at 12.000
15.000 10.000
30,000 22,000
31.000 25,000
31,000 26,000
70,000
rupture) (psi)
Flexural strength (at yield) 11.000
17,000 11.000
14,000 7,000
14,000 7,000
14,000 15.000
60,000
(psi)
Elongation (at break) (%) 1.5
2.0
0.4
0.8 0.4
0.8 0.1
0.2
Hardness (Rockwell) M93
120 M124
128 E64
95 M100
115 E54
101
Heat deflection temperature 165
175
300
350 300
370 350
600
(at 264 psi)(°F)
Coefficient of linear thermal 1,700
1,800 640
1,520 30
45 30
45 8
21
expansion 1026 (in./in. °C)
Thermal conductivity 1024 3
5

4
8 8
14
(cal/sec cm °C)
Linear mold shrinkage (in./in.) 0
0.01 0
0.01 0.004
0.006 0.004
0.009 0.001
0.004
Dielectric strength (V/mm) 250
400 200
350 300
380 260
400 140
400

Dissipation factor (at 60 Hz) 0.10
0.15 0.06
0.10 0.04
0.20 0.03
0.3 0.01
0.1
( 5 1 KHz)
Water absorption (24 H)(%) 0.2
0.4 0.1
0.2 0.05
0.9 0.3
1.5 0.03
1.2
Specific gravity 1.236
1.320 1.25
1.30 1.37
1.46 1.30
1.35 1.69
2.0

Conversion factors: 1 psi 5 0.006895 MPa.
22 HANDBOOK OF THERMOSET PLASTICS

Table 2.3 Typical Formulations of Phenolic Molding Resins

General-purpose High-impact Electrical Grade (Pipe) Coating

Composition (phr) Grade Grade (Insulation) Grade
Novolac/resin 100 100 100 100
HEXA 15.0 15.0 15

Wood flour 120



Fabric shreds
150


Fiber glass

40

Mica

120

Lime/magnesium 2.0 2.0 2.0 5.0
oxide
Clay


5.0
Magnesium stéarate 2.0 3.0 2.0

(lubricant)
Plasticizer


10.0
Colorants (dyes or 4.0 3.0 3.0 73.0 (iron oxide)
pigments)
Alcohol


55.00

phr: parts per hundred resin.

There are several types of phenolic molding
resins: [3,22]
1. General-purpose grade (wood flour filled).
2. Non-bleeding grade (resole based, glass filled).
3. Heat-resistant grade (mineral filled, mica).
4. Impact grade (cellulose, rubber, glass, fabric
filled).
5. Special or electrical grade (mica, glass filled).
Phenolic molding resins are generally made of two-
3. High creep resistance. The high dimensional
stage novolacs, although some are made of resoles.
The properties of phenolic molding resins include:
1. Ease of molding. Phenolic resins can be eas-
ily molded into intricate shapes and to fin-
ished dimensions with little or no extra
finishing touches.
2. Very good dimensional accuracy and stability.
Phenolic molding resins have very good
dimensional accuracy and stability at normal
atmospheric conditions. Their linear mold
shrinkage is 0 to 0.01 in./in. and their filled
compounds have a coefficient of linear thermal
expansion of about 8 to 45 3 1026 in./in. °C.
Typically, molding compounds based on
novolaks are twice more dimensionally
stable than resole-based molding com-
pounds. Novolak-based compounds are more
stable because they give off ammonia upon
curing, while resole-based compounds give
off water. The water molecule is larger than
the ammonia molecule. The glass-filled
resins are more stable than the cellulose-
filled types. The lower the cellulose content,
the more stable the resin.
stability of phenolic resins is complemented
by their high creep resistance [23]. Data
from Materials Engineering, Manual 249,
September 1974 indicate that phenolic
resins, in comparison with engineering ther-
moplastics such as polycarbonate, polyace-
tal, and polyphenylene oxide, have very high
creep resistance. When tested at 2000 psi,
73°F, and over 400 hours, the maximum total
strain (%) for phenolic resin is less than 0.1
compared to more than 0.4 for polycarbon-
ate, more than 0.6 for polyphenylene oxide,
and more than 1.4 for polyacetal.
2: PHENOL
FORMALDEHYDES
4. High deformation resistance under load.
Phenolic resins have high resistance to
deformation under load. Flexural and com-
pressive strengths for general-purpose phe-
nolic molding resin are 7,000 to 14,000 psi
and 25,000 to 31,000 psi, respectively.
5. Good heat resistance. Phenolic molding
resins have low thermal conductivities and
are good heat insulation materials. The ther-
mal conductivity of general-purpose phenolic
resin is about 4 to 8 3 1024 cal/scc cm.°C.
Its heal deflection temperature (HDT) is
about 300 to 370°F.
6. Good electrical resistance. Phenolic molding
resins are good electrical insulation materi-
als, with a dielectric strength of 260 to
400 V/mm and a dissipation factor of 0.03 to
0.3 for general-purpose grades. They are most
suitable for low voltage (260 to 400 V/mm)
electrical insulation.
7. Good chemical resistance. Phenolic molding
resins are resistant to common solvents,
weak alkalis, weak acids, hydrocarbons, and
detergents, but are attacked by strong alkalis
and concentrated oxidizing acids.
8. Low water absorption. Water absorption of
phenolic molding compounds is only about
0.03 to 1.75%. The resole-based molding
resins are more water resistant. Un-
preheated preforms (loose powder form)
tend to absorb more water under humid con-
ditions and will lose moisture and stiffen in
low moisture or dry conditions such as in
winter. It is recommended that phenolics be
stored at room temperature and 50 to 60%
relative humidity.
9. Good weather resistance. Phenolics can be
used outdoors for short periods, but pro-
longed outdoor exposure to ultraviolet-light
and heat can cause failure.
10. Good machining qualities. Machining quali-
ties are fair to good for molding compounds,
but are excellent for casting resins.
Fillers for Phenolic Resins
The properties of phenolic resins can be
enhanced by the use of fillers and additives; the
type of filler used depends on the application(s) for
23
which the material is formulated. The fillers typi-
cally used with phenolic resins are:
1. Wood flour. This is made from pine and
spruce wood chips that have been chemi-
cally treated to remove the lignin. Wood
flour, the least expensive of the fillers, has
high-volume usage and provides good flow
and appearance, low-heat conductivity, good
tensile strength, and poor impact strength.
2. Cellulose (cotton flock). It is typically used
for good impact strength.
3. Mineral fillers (asbestos, mica, and clay).
Asbestos is no longer used as a filler
because it is a suspected carcinogen. Mica is
complex potassium/aluminum silicates
(K2AL4)-(AL2Si6O20)(OH)4 made from the
minerals muscovite and phlogopite. It has
good electrical and heat insulation proper-
ties, and dimensional stability. It does not
wet well and sticks in the mold; it needs to
be used with a wetting agent such as sodium
stearate, sodium lauryl sulfate, sodium lig-
nin sulfonate, or silicone coupling agents.
The wetting agent reduces interfacial tension
between filler and resin. Mica dust is toxic
and must be handled with care. The auto
industry uses mica as an inexpensive substi-
tute for fiberglass in polypropylene and phe-
nolic parts. Clay is a form of aluminum
silicate used to enhance heat and chemical
resistance, dimensional stability, and viscos-
ity control. Its dust is toxic and must be han-
dled with care.
4. Silica (SiO2). It is natural crystalline sand,
quartz, and diatomaceous earth, although
synthetic, non-crystalline, amorphous forms
exist. It is used for its abrasive, electrical and
heat insulation properties, viscosity enhance-
ment, and shrinkage and crack reduction.
5. Graphite fiber. Produced from the pyrolysis
of stretched polyacrylonitrile or rayon, it has
more than 99% carbon content (less than
97% carbon content 5 carbon fiber). It is
used to improve strength and frictional prop-
erties (lubrication). It is relatively expensive
(Figures 2.2 and 2.3).
6. Glass fiber (fiberglass). It has a composition of
55% silica, 20% CaMg oxides, 14% alumina,
24
Figure 2.2 Hercules chopped graphite fibers for
compression and injection molding. (Courtesy of
Hercules Advanced Materials & System Company.)
Figure 2.3 Hercules continuous graphite fibers for
pre-pregging and filament winding applications.
(Courtesy of Hercules Advanced Materials &
System Company.)
10% borates, and 1% sodium and potassium
oxides. It is used to improve impact strength,
heat, and electrical insulation properties.
7. Talc. This mineral filler is a form of hydrated
magnesium silicate (3 MgO•4SiO2•H2O)
used to enhance stiffness, creep resistance,
and heat resistance.
8. Fabric fibers (sisal, rag fibers). Sisal is a
form of natural fiber from Africa and Haiti
HANDBOOK OF THERMOSET PLASTICS
used in rope making. Rag fiber is derived
from textile materials. These fillers improve
impact strength and produce a rough surface
when machined, properties necessary or
desirable in “no-slip” surfaces as in pulley
belts and ropes.
9. Synthetic fibers (orlon, nylon, teflon). These
fillers provide improved impact and tensile
strengths and vibration dampening.
10. Paper. This filler is typically used for elec-
trical insulation properties.
11. Polyaramid fibers (aromatic polyamide
fibers). Two popular types of polyaramid
fibers, Kevlar and Nomex, are trade names
of DuPont. Kevlar is an organic reinforcing
fiber with high tensile strength and modulus
used mainly in advanced composites.
Nomex is valued mainly for its heat and
electrical properties. Aramid/phenolic com-
posites are used extensively in aerospace
interiors owing to their high strength-
to-weight ratios and heat resistance.
A combination of fillers is commonly used to
achieve optimum property enhancement. Fillers
also have a direct effect on the shrinkage of molded
phenolic parts. Polyaramid fibers give the least
mold shrinkage; synthetic fibers give the most.
There is also a direct correlation between mold
shrinkage and the coefficient of linear expansion
(Table 2.2). Fillers are also used to reduce cost and
exotherm.
Processing Methods for Phenolic
Resins
The three major processing methods are com-
pression molding, injection molding, and transfer
molding. Other forms of processing, such as run-
nerless injection compression (RIC) and casting,
are becoming popular. (RIC is a registered trade-
mark of Durex.) Compression molding is the origi-
nal processing method for phenolic resins per Leo
Baekeland’s “heat and pressure” patent. Still the
most popular method in use today, produces the
strongest, most dimensionally stable products
because less damage is done to the fibrous fillers
and shrinkage is low. Warpage is less because
pressure is applied evenly, and internal stresses
are minimized. The molds are infrared- or
2: PHENOL
FORMALDEHYDES
radiofrequency-healed and the correct amount of
resin is put into the cavity. The molding is carried
out under pressure. Compression molding cannot
handle delicate inserts, and flashing is common.
Compression molding temperature and pressure
conditions for phenolic resins are typically in
the range of 290
400°F and 2,000
20,000 psi,
respectively.
Transfer molding is popular for applications
involving delicate inserts. This process involves
using a separate heated transfer charger from which
a pre-heated, pre-weighed resin is pushed into the
mold by an auxiliary ram or plunger. Transfer
molding is also used for parts with both thin- and
thick-walled sections.
Injection molding [24,25] of phenolic resin is
similar to that of thermoplastic resins. Technological
advances, such as availability of glass-filled, injec-
tion molding grade phenolic resins and use of screw
(reciprocating) injection molding process, have
made injection molding of phenolic parts economi-
cally feasible and desirable. In screw injection mold-
ing, the material is preheated, plasticized via
frictional heat, conveyed, and injected into a closed
mold by the screw action and movement. Direct
and automatic feeding of the material to the mold
eliminates the preforming steps (storage and pre-
heating), thereby reducing process cycle time and
increasing productivity. The higher mold tempera-
tures (320
380°F), high frictional heat, and faster
injection speed of the process require adequate vent-
ing. Processing pressures and material temperatures
for the screw injection molding process of phenolic
resins are 10,000
20,000 psi and 220
240°F,
respectively.
RIC molding [25] is a new process invented by
Durez. RIC combines the direct and automatic
feeding action of injection molding and the dimen-
sional stability of compression molding. The low-
pressure injection process introduces the material
into a partially open mold (1/4 to 1/2 in.), and the
compression portion of the process takes place with
the closing of the mold. This combination results in
such advantages as speed (faster process cycle
time) and the dimensional stability of molded parts.
Also, because the mold is open during “mold fill,”
venting and mold staining problems are reduced.
The runnerless system makes for lower scrap level
and material savings.
Casting of phenolic parts makes the case for pro-
cessing and cost-effectiveness, especially for profile
25
shakes such as bowling balls, billiard balls, cutlery
handles, and specialty items.
Applications of Phenolic Resins
[2,3,23,25
30]
Trends in the consumption of phenolic resins are
presented in Table 2.4. There are five major areas
of phenolic resins application: adhesives and bond-
ing (these being dominated by wood adhesives,
97%; Foundry binders, 3%), laminates, molded
parts, and coatings. Wood adhesives and laminates
are part of the adhesive and bonding market, but
the large volume usage of phenolic resins in wood
adhesives (in 2004 69% of the phenolic resin mar-
ket) and laminates (7%) warrant their consideration
as distinct areas of application of phenolic resins.
Phenolic resins for insulation also reached 13% of
the market in 2004
Phenolic Resins in Plywood
[2,3,23]
Plywood belongs to a class of materials referred
to as composite wood materials or wood resin
boards. The other wood products included in this
category are particle board, fiber board, wafer
board, and strand board. Phenolic resins serve as
the bonding material in these products. Table 2.5
presents the typical resin formulations for the adhe-
sives used for composite wood materials. These
composite products other than plywood (particle
board, fiber board, wafer board, and strand board)
are considered part of the adhesive and bonding
market and are treated as such in Table 2.4.
Together, these fibrous and granulated wood pro-
ducts and plywood account for 69% of the phenolic
resins market in 2004 (compared to 49% for ply-
wood alone in 1993).
The use of phenolic resins in plywood was intro-
duced into the U.S. in 1932 with the importation of
the Goldschmidt glue line (“Tego film”) from
Germany. Tego film is a thin sheet of paper
impregnated with phenolic resin. Typically, the thin
sheets of paper are placed between layers of veneer
(wood), and the layers of veneer are hot pressed at
temperatures of 100
150°C and pressures of
700
6000 psi. The use of phenolic resins (in Tego
film) in plywood was a response to the demand for
exterior weatherproof plywood. Prior to the intro-
duction of Tego film, the bonding materials for
26 HANDBOOK OF THERMOSET PLASTICS

Table 2.4 Trends in Phenolic Resins Consumption (1983
2004) (106 lb/yr)

Wood and
Foundry Molding Protective
Year Adhesives Laminates Composites Coatings Insulation Others Total

1983 1750 134 200 20 116 2230

1984 1948 149 238 22 145 2502

1985 2005 142 209 23 256 2640

1986 2010 167 195 22 269 2662

1987 2326 193 197 23 268 3007

1988 2452 213 198 21 367 3053

1989 2221 246 176 13 170 2826

1990 2374 197 168 17 182 2938

1991 2071 157 160 16 259 2663

1992 2308 176 173 17 283 2957

1993 2431 173 163 13 290 3070
2004 3384 329 235 17 611 141 4717

Data not available.

Table 2.5 Typical Formulations for Adhesives Used in Composite Wood Products

Composition (phr) Plywood Particle Board Fiber Board

Phenolic resin 100 100 100
Water 0
20 50
110 0
120
Filler 5
10
Extender 0
10
Hardener (CH2O) 0
5.0 0.2
0.5 0
0.5
Solubilizer (NaOH) 3
10 8
12 5
10
Fungicides/Insecticides 2
4 2
5
Process temp (°C) 100
150 160
220
Process pressure (psi) 730
5880 290
590

phr 5 parts per hundred resin.

plywood were casein glue, peanut meal, and soy-
bean meal, which are strictly for interior use. The
adhesive material for exterior grade plywood is
resole-type phenolic resin with a swell-resistant
filler such as coconut shell. Other fillers used are
oat hulls, wheat flour, and chalk. Wheat flour and
chalk are mainly used as extenders for adhesive-
ness. The extenders are also used to reduce cost
and porosity. Sodium hydroxide serves as a solubi-
lizer in phenolic resin in water.
Phenolic resins compete very favorably with
urea
formaldehyde-bonded plywood, and most of
the plywood made today is phenolic resins based.
The lack of homogeneity in wood composition is a
problem in the production of plywood. The degree
of penetration or saturation of the wood by the
resin determines the level of bonding. It is custom-
ary for plywood manufacturers to carry out tests
and experimentation to determine the right resin
formulation for each wood or veneer system.
2: PHENOL
FORMALDEHYDES
Phenolic resin-based plywoods find application in
the making of interiors and parts for automobiles,
boats, ships, trucks trains, machines, and tool han-
dles. Some of the luxury cars, such as Mercedes and
Cadillacs, use plywood for dashboard decoration.
Other Composite Wood Products
The consumption of phenolic resin-based com-
posite wood materials (fibrous and granulated
wood) has increased dramatically, passing from
1989 to 1993 and 2004 (Table 2.4).
Particle Board. This composite wood product,
commercially introduced in the USA in 1941, con-
sists of about 10% resin and 90% wood chips (saw
dust, plywood scraps, planer shavings). The percen-
tages vary depending on the number of layers of
the product. The resin, which wets and binds the
wood material, improves the relative humidity of
the wood
resin blend from about 5% to about
15%. The blend is prepressed at room temperature
and 145 to 140 psi, and ultimately compressed at
160
220°C and 290
590 psi, depending on the
desired density of the product. The steam released
during the process acts as the heat-transfer medium
(steam shocking). The boards produced are post-
cured by hot stacking them in storage. The strength
of the boards produced depends on the type and
structure of the wood chips used and the resin for-
mulation. Particle boards with higher resin contents
have higher bonding strength. Particle board is pre-
dominantly a urea
formaldehyde-based product,
with phenolic resin-based particle board products
accounting for only about 10% of the particle board
market. Particle board is used in the construction of
furniture core, floor underlayers, prefabricated
housing, freight cars, and ships. Fungicides and
insecticides such as tributyl tin oxide are added to
the resin formulation to enhance the resistance of
particle board to fungi and insects.
Wafer Board. This material is a type of particle
board with large wood chip sizes of up to 0.008 m
thick, 0.0015 m wide, and 0.0075 m high. Phenolic
resin is the predominant bonding material. Wafer
board is used mainly used for exterior structural
applications.
Fiber Board. This material is a paper-based phe-
nolic resins bonded composite material used for
heat and sound insulation. The paper sheets are
derived from lignocellulosic fibers and generally
are more than 1.5 mm thick. The paper sheets are
27
typically self-bonding, but adding phenolic resin
reduces water absorption and swelling, and
improves strength. Fiber boards can be classified
according to their density. Those with densities of
0.02 to 0.40 g/cm3 are known as non-compressed
fiber boards; those with densities in the range of
0.60 to 1.45 g/cm3 are classified as compressed
fiber boards. Examples of non-compressed fiber
board are semi-rigid insulation board (0.02 to
0.15 g/cm3) and rigid insulation board (0.15 to
0.40 g/cm3). Examples of compressed fiber boards
are medium-density fiber board (MDF, 0.60 to
0.80 g/cm3), high-density fiber board or hard board
(HDF, 0.90 to 1.20 g/cm3), and special densified
hard board (1.20 to 1.45 g/cm3). The American
Plywood Association has done a lot of research in
the area of fiber board manufacturing.
Strand Board. This material is also a phenolic
resin-based composite board product that is used
extensively in exterior and structural applications.
Reactivity and Hardening
Reactions of PF Wood Adhesive
Resins
PF adhesives for the core layer of panels usually
have the highest average molar mass and hence
show higher reactivity and quick gelation. They
contain a higher proportion of alkali than face layer
resins in order to keep the resin soluble even at
higher degrees of condensation. The higher the
degree of condensation during the production pro-
cess (the higher the viscosity), the shorter the gel
time [31]. The limits of the increase of the degree
of condensation in the production process of the
resin is given by (i) the viscosity of the resin (the
resin must be able to be pumped to have a certain
storage stability as well as a proper distribution
of the resin on the particles during blending), and
(ii) the flow behavior of the resin under heat,
guaranteeing wetting of the unglued second wood
surface and a sufficient penetration into the wood
surface. Decreasing the solid content of the resin is
limited by a possibly too-high moisture content of
the glued particles.
Alkaline PF-resins contain free-reactive methylol
groups in sufficient number and can harden even
without any further addition of formaldehyde, of a
formaldehyde source, or of catalysts. The hardening
reaction is only initiated by heat. The methylol
28
groups thereby react to methylene and methylene

ether bridges. At higher temperatures ether bridges
can rearrange to methylene bridges. The lowest
possible temperature for a technically sufficient
gelling rate is approx. 100°C. In some cases potash
in the form of a 50 mass% solution is added to
the core layer resin mix in an amount of approxi-
mately 3
5% potash solid based on resin solid
content.
An in depth investigation of the dependence of
the gel time of an alkaline PF
resin from the pH
[32] surprisingly found an unexpected lengthening
of gel time in the very high pH region (above 10).
There are exactly such pHs, however, which are the
ones used for commercial PF resins for wood, with
a content of NaOH of 5 to 10% by mass. The pH
of the resin, however, may well change when the
resin comes into contact with the acid wood surface.
Especially with rather acid wood species, the pH of
the resin could significantly drop [33], bringing the
resin back to the pH of its highest reactivity.
It has also been shown that lignocellulosic sub-
strates have a distinct influence on the hardening
behavior of PF-resins [34,35], of all the other
formaldehyde-based adhesives, and of other ther-
mosetting wood adhesives (such as isocyanates):
the activation energy of the hardening process is
much lower than for the resin alone [35]. The rea-
son for this is a catalytic activation of PF and other
resin condensation by the surface of polymeric
wood constituents, in particular carbohydrates like
crystalline and amorphous cellulose and hemicellu-
lose. Covalent bondings between the PF-resin and
the wood, especially lignin, do not play any role
under the conditions industrially prevalent today for
wood adhesives application [35].
The acid-induced gelling reaction of PF resins
can instead cause severe deterioration of wood and
therefore has lost more or less completely its
importance in the wood panels field. Procedures for
the simultaneous neutralization of acid-hardened
PF-glue lines during their curing have also been
described [36]. These work by adding to the PF
glue-mix a strong acid coupled by complexes of
morpholine and a weak acid. After hot curing the
complex that reforms is between the morpholine
and the strong acid, almost neutralizing the glue-
line and preventing acid deterioration of the wood
substrate.
Acceleration of the hardening reaction is possi-
ble by using a resin with a degree of condensation
HANDBOOK OF THERMOSET PLASTICS
as high as possible. A more effective PF-
accelerating system is the addition of esters such as
propylene carbonate [32,37
42], or even better, of
glycerol triacetate (triacetin) [15,32,43] or guani-
dine carbonate [43]. The higher the addition of
ester, the lower the gel time of the PF-resin [32].
Esters not only accelerate resin curing, but also
increase the ultimate strength of the cured resin,
indicating that a more cross-linked, hardened net-
work has been obtained.
Potassium carbonate, sodium carbonate [37,41,42],
or sodium and potassium hydrogen carbonates are
instead just accelerators of PF resin curing, and don’t
contribute to an increase in strength of the hardened
network [37]. Also, wood extractives such as flavo-
noid tannins [1], other wood chemicals [41], and
amines [37] have an accelerating effect on the hard-
ening of PF-resins.
A further, very effective, and relatively inexpen-
sive manner for accelerating the hardening of PF
adhesives is by either partly co-polymerizing them
with urea during or after their preparation (see
below).
Since alkaline phenolic resins harden only by
heat, post-curing of wood panels during hot stack-
ing is important. Opposite to UF-bonded boards,
PF-bonded boards should be stacked as hot as pos-
sible to guarantee a maximum post-curing effect.
However, too high a temperature during stacking
might start to cause some wood degradation.
Some special resins consist of a two-phase sys-
tem with a highly condensated and no longer solu-
ble PF-resin and a usual PF-resin [44]. Another
two-phase resin is composed by a highly conden-
sated PF-resin still in an aqueous solution and a
PF-dispersion [45]. The purpose of such special
resins is the gluing of wet wood, where the danger
of over-penetration of the resin into the wood sur-
face can cause a starved glue line.
Phenolic Resins in Adhesive
and Bonding Applications
Phenolic resins totaling 2.4 billion pounds went
into the adhesive and bonding markets in 1993
(Table 2.3); this increased to more than 3.5 billion
pounds in 2004, making the adhesive and bonding
market the largest outlet for phenolic resins. It is
arguable that the adhesive and bonding market
includes the composite wood and laminating appli-
cations because phenolic resin is the bonding
2: PHENOL
FORMALDEHYDES
material in these applications. Table 2.4 indicates
that phenolic resins in adhesive and bonding appli-
cations include, other than wood adhesives:
1. Insulation materials.
2. Fibrous and granulated wood.
3. Foundry and shell molding.
4. Friction materials.
5. Bonded and coated abrasives.
Phenolic Resins as Insulation
Materials
The low thermal conductivities of plastics in gen-
eral and phenolic resins in particular make these resins
good heat insulators. The thermal conductivity of phe-
nolic resins ranges from 3
15 3 l024 cal/cm.°C
(Table 2.1).
It also accounts for the strong competition that
phenolic resins are experiencing in the insulation
market from other plastics such as polyurethanes
and polystyrenes. Phenolic resins totaling 366 mil-
lion pounds were used as insulation materials in
1993, reflecting an 11.6% decrease from the 1989
consumption volume of 414 million pounds. The
366 million pounds of phenolic resins consumed in
the insulation market in 1993 represent a respect-
able 12% share of the total phenolic resin market.
Three major forms of phenolic resin-based insula-
tion materials are in use: mineral fibers, phenolic
foams, and fiber mats. The mineral fibers and phenolic
foams used for heat insulation are typically aqueous,
have low-solids content, and are resole-based. The
fiber mats (textile) are novolac-based (with about 10%
HEXA as the curing agent) and are used mainly for
sound or acoustical insulation. Glass wool (fiber glass)
and rock wool are the most common mineral fibers.
The production of mineral fiber insulation
involves spraying the hot mineral fibers with an
aqueous resole solution and healing the resolc-
soaked fibers al about 200°C to cure the resin. The
resin content of mineral fiber insulation is typically
less than 10%, with the fiber accounting for 90% or
more of the insulation material composition. The
production of phenolic resin foam requires the use
of blowing agents and water-soluble surfactants to
control the size of foam cells.
These phenolic resin insulation materials have
characteristic flame resistance, low smoke generation,
29
low thermal conductivity, and high temperature resis-
tance. Phenolic resin foams are good heat insulators
up to 120°C, whereas glass wool and rock wool are
good insulators up to 260°C and 385 °C, respectively.
The added superior moisture resistance qualities of
glass wool, in spite of its higher cost, make it the pre-
ferred material for low-temperature home and resi-
dential insulation where moisture permeation is a
constant problem. The higher operating temperature
of rock wool makes it the material of choice for
industrial-type insulation, such as for pipes, reactor
vessels, and boilers. About 80% of phenolic resin
insulation is glass wool-based, and 10% is rock wool-
based. Some phenolic resin foams and mineral fibers
are used in sound insulation, but the predominant
choice material for sound insulation is fiber mat.
Phenolic resins fiber mats are used for reduction and
control of sound in automobiles, offices, auditoriums,
and industrial plants.
Phenolic Resins in Friction
Materials [2,3]
Friction materials refer to brake linings and
clutch facings. Grinding wheels, cut-off wheels,
emery paper, scrub and scouring pads, and fiber
discs, typically classified as bonded and coated
abrasives, are also friction materials. The consump-
tion volume of phenolic resins as friction materials
during 1993 was 73 million pounds (including 26
million pounds for bonded and coated abrasives) or
2.45% of the total phenolic resins market.
Brake linings are used especially in the transporta-
tion, automotive, aircraft, railroad, and trucking
industries. Other heavy users of brake linings are the
drilling (oil, water wells) rigs and construction
(cranes, fork lifts) industries. While the Society of
Automotive Engineers has standard test methods for
brake linings, most brake lining manufacturing opera-
tions are customized to fit the specific end usage
requirements. “The family car requires a relatively
soft lining for easy brake control, quiet action and
good friction. The taxicab or bus requires long-
lasting linings. A heavy duty truck requires excellent
heat resistance and long life.” [3]. Hence, the compo-
sition in friction materials varies. Typically, the phe-
nolic resin used is either resole or novolac-based, but
is rubber-modified for elasticity and toughness.
Asbestos had been the choice of reinforcing filler
30
(300 phr), but was discontinued because it is a sus-
pected carcinogen. Mica, tale, or fiber glass are the
choice fillers for replacing asbestos. Graphite is used
as a lubricant (40 phr), and powdered metals
(200 phr) are used to improve thermal conductivity.
Wear resistant additives, such as cashew nut shell liq-
uid plus formaldehyde, cure reaction in pulverized
form, are used to the tune of 50 phr.
Bonded and Coated Abrasives
Grinding wheel and emery paper are the major
outlets for phenolic resins in bonded and coated
abrasives. Leo Baekeland introduced the first phe-
nolic resin-bonded grinding wheel in 1909. Today,
phenolic resin-bonded grinding wheels are the
most popular type of grinding wheel. They have
replaced ceramic wheels to a large extent, mainly
due to the enhanced performance of phenolic
resins. Phenolic resin bond is more thermal, water,
and mechanical shock resistant than other bonding
materials such as powdered clay and rubber. Also,
these grinding wheels have higher tensile strength
and can operate at higher speeds and remove metal
more efficiently. Contrary to popular impression,
grinding wheels are used more in industry than in
home workshops. Steel manufacturing and fabricat-
ing plants are the biggest users of grinding wheels.
A grinding wheel “18 inches in diameter and 0.1
inch thick can slice a 1-inch bar of steel in a few
seconds leaving a mirrored finish.” [3]
A grinding wheel consists of three parts: the grit
or abrasive grain, bonding material, and fillers.
The two most commonly used grits for these
wheels are synthetic fused alumina made from
hydrated aluminum oxide (bauxite, A12O3•H2O)
and silicon carbide (SiC) obtained from the high-
temperature (2000°C) reaction of silica (sand) and
coke in an electric furnace. The grit has a grain
size of 20 µm to 3 mm. Alumina-based wheels,
being tougher, are used for grinding high-strength
products such as steel. Silicon carbide is harder and
is used for grinding hard and brittle materials such
as glass, ceramics, stone, and cast iron.
The bonding material is alkaline catalyst-cured
liquid resole-based phenolic resin. Sometimes a
combination of liquid resole-based and powder
form novolac-based phenolic resins is used to
enhance performance. Low-solids, low-viscosity
phenolic is preferred for improved shelf life.
Toughness and elasticity can be enhanced with
HANDBOOK OF THERMOSET PLASTICS
modified phenolic resins. Phenolic resins can be
modified for low flow by being co-curing with
epoxy resin or polyvinyl butyral (interpenetrating
network resins, IPNs).
Common fillers for grinding wheels are alumi-
num oxide, iron oxide, silicates, and chalk. (The
use of asbestos as a filler has been discontinued.)
Typical formulation for a grinding wheel is as fol-
lows: resole phenolic resin (1/m 100 parts per hun-
dred resin, phr), novolac phenolic resin (1/m
250 phr), grit (1/m 1500 phr), filler (1/m 200 phr),
and curing agent/accelerator (calcium or magne-
sium oxides, 1/m 15 phr).
Emery paper is a polishing material that has
largely replaced animal hide glue-bonded sandpa-
per. Emery is an impure corundum (naturally
occurring alumina, A12O3) mixed with iron oxide
that serves as the grit or abrasive material in emery
paper. The substrate or backing material is rubber
or acrylic-modified paper, and the bonding material
is phenolic resin (resole or novolac-based).
Sometimes combinations of phenolic resins and
animal glue are used. Emery paper is used primar-
ily for wet-polishing automobile body coatings.
Phenolic Resins in Foundry
and Shell Molding Applications
[2,3,22,46,47]
Foundry and shell molding applications account
for about 3% of the total phenolic resins market,
with about 140 million pounds’ consumption vol-
ume per year in 2004. Phenolic resins and blends
are used as the binding material for sand-based lost
core molds. Lost core molding and permanent mold
processes are two major ways to cast metals.
Permanent molds, usually made of metals, cera-
mics, or graphite, are used in mass production die
casting of low melting metal alloys. Lost core
molding is used for the precision molding of nov-
elty items, such as jewelry, and specialty products,
such as titanium-based jet turbine blades and parts
or products that have metal-free volumes as part of
their profile. The automotive, steel, construction,
and machine parts industries are major users of lost
core molding. The engine block, with its cylinder
holes and the cylinder head water jacket section, is
a good candidate for lost core molding.
Lost core molds are typically made of wax or
plaster of Paris and sand. The sand-based lost core
2: PHENOL
FORMALDEHYDES
mold uses phenolic resins and other binder materi-
als such as polyurethane, urea-based resins, oils,
starch, clays, and gypsum. The inorganic binders,
gypsum (cement), and clays do not meet the dimen-
sional stability, high-strength, and high-speed pro-
duction rates requirements for metallic castings.
This and other post-mold processing requirements,
such as finishing, have made phenolic resins and
blends the preferred binding materials for sand-
based lost core molds. Commonly, phenolic resin
blends are phenolic resin/polyurethane and phenol/
UF resins. The sand core bonded with inorganic
binds tends to produce parts with poor finishing,
and post-mold machining is very high.
Four major lost-core molding processes are in
use: shell molding, cold box, hot box, and no-bake.
Shell Molding Process
J. Croning invented the shell molding (Croning)
process in Germany in 1944 and introduced it in
the United States in 1949. The process uses novolac-
type phenolic resin as a binder. In the process, the
resin-coated sand is put into a mold of the desired
shape or heated metal pattern at about 270°C. The
mold is usually treated with a mold release agent
(usually a silicone type) before the resin-coated sand
is put into it. The melting and fusion of the resin
binds the sand grains and forms a solid shell. The
desired thickness of the shell mold is achieved by
controlling the cure rate of the phenolic resin/blend,
mold temperature, and residence or cure time. The
automobile industry favors the shell molding process
for the manufacture of crankshafts, cam shafts, and
engine valves.
Cold Box Process
The cold box process popularized by “The
Ashland Process” uses a two-component thermoset-
ting hybrid system of phenolic resin (IsoCure I)
and Polyurethane (IsoCure II) as the binder. The
IsoCure binder with amine catalyst, such as triethy-
lamine (TEA) or dimethylethylamine (DMEA), pro-
duces a flowable sand mix that is easily blown or
shot into the core box. The sand/phenolic resin/
polyurethane (sand plus IsoCure) mix cures at room
temperature to produce the core or mold, depending
on the particular application.
The room temperature cure of the cold box pro-
cess results in energy savings and warpage- and
31
shrinkage-free casting. Also, the cores or molds
ejected from the box or pattern, respectively, are
almost completely cured and dimensionally accu-
rate, so core and pattern scrap is reduced.
Trends in Foundry and Shell
Molding
The laboratory operations of Pittsburg State
University’s Kansas Foundry and Manufacturing
Technology program epitomize the current trends in
the foundry and shell molding industry. The foundry
program, one of the 26 Foundry Educational
Foundation affiliated programs in the U.S., uses a
blend of some of the most current technologies and
traditional foundry and shell-molding processes in
investment casting activities. Professor Russell
Rosmait, who teaches the foundry courses, has
invested in casting activities that use plastics-based
(wax) prototypes produced by a CAD-driven
Stratasys (fused deposition modeling) equipment as
the core or pattern for making molds. Rosemait’s
laboratory also has a Palmer mixing machine, which
has provisions for metering and mixing the two-
component (phenolic resin and Polyurethane) binder
system, and a WSF Industries, Inc.-certified steam-
type autoclave. This Pittsburg State University labo-
ratory uses aluminum, iron, steel, or bronze to pro-
duce parts such as the University’s nameplates,
bookends, and Stratasys-designed parts (engine parts,
piston, clutch parts).
Phenolic Resins in Laminating
Applications
The 2004 consumption volume of 329 million
pounds for phenolic resins in laminating applica-
tions, when compared to the 1989 figure of
246 million pounds or the 1983 figure of 134 mil-
lion pounds, reflects the gradual but steady loss of
the competitive edge of phenolic resins in the plas-
tics laminating market. This loss of market share
represents the strong presence of engineering ther-
mosets such as polyurethanes and epoxy resins.
Phenolic resins in laminating applications are
used mostly in the building, furniture, electrical,
and electronics industries. Specifically, laminates are
used in printed circuit boards, laminated tubes and
rods, decorative laminates, filters, separators, and
molded parts.
32
A laminate essentially consists of a substrate
(support material) and an impregnating material. In
phenolic-resin-based laminates, the impregnating
material is phenolic resin or phenolic resin blends,
and the substrate is typically a cellulose-based fiber
such as cotton fiber or paper fiber. Two paper sub-
strate types are common, especially in electrical
laminates: cotton linter paper and Kraft paper.
Cotton linter paper is easier to impregnate and has
better electrical properties and punchability. Kraft
paper is less expensive and has greater mechanical
strength. Cotton fiber, used in high-strength lami-
nates, is stronger than paper.
The substrate is generally impregnated in two
steps (cotton linter paper requires only one step).
The first step uses low-molecular-weight phenolic
resin (about 300), and the second uses medium
molecular weight resins. It is easier for the low-
molecular-weight resins to penetrate the pores of
the substrate. The resin formulation varies, depend-
ing on the end use of the laminate. Laminates for
electrical applications need phenolic resins of low
inorganic ion content. Hence, only deionized water
must be used in such applications. The phenolic
resin-impregnated substrate is cut to size, stacked
to achieve the right thickness, and cured in a press
at about 170
190°C and 2000 psi.
Typically, paper-based electrical laminates are
used mainly for making the circuit board in printed
circuit boards for radio and other electronic equip-
ment. The laminate circuit board is completely cov-
ered with copper for ease of printing the conductor
network. Thus, the laminate board serves as a sup-
port and insulation in printed circuit boards. These
boards are also used for switchboards, switch gear
insulating washers, and aircraft pulley wheels.
Laminated tubes and rods are made from both
paper and cotton fibers and are typically used to
insulate machine parts, mainly because of their
high dielectric strength. They also have a very high
strength-to-weight ratio. Their other applications
include winding support for transformers, bobbins,
and guide rolls for paper and textile machines. The
tube shapes are produced by core molding: the core
is removed after molding, and the tube laminate is
cut to size via machining.
Cotton fiber laminates have high strength, heat
resistance, excellent moisture barrier, and very good
resistance to lubricants, acids, weak alkalis, and sol-
vents. They are commonly used in construction and
electrical insulation applications. Wheel bearings
HANDBOOK OF THERMOSET PLASTICS
and switch-based plates, bushings, and gears are
examples of products made with cotton-fiber lami-
nates. Some glass-phenolic resin grades are avail-
able, such as Westinghouse Electric Corporation’s
Micarta resins used as gaskets and seals, which offer
electrical, moisture, and temperature resistance.
Decorative or high-pressure laminates, the most
popular type of phenolic resin-based laminates, find
major application in the furniture industry. “Formica,”
a trade name for a decorative laminate produced by
Formica Corporation, a subsidiary of American
Cyanamid Company, is used for chemical scratch- and
heat-resistant surfaces. Oilier forms of decorative lami-
nates made by other companies abound, especially for
countertops and wood veneers. Decorative laminates
in general are used for lamination of particle boards
and wood materials used in furniture construction.
The other major phenolic resins-based lamina-
tion products are filters and battery separators.
Oil, fuel, and air filters [2,3,48] for the automotive
and building industries are made from filler-free
paper impregnated with phenolic resin. The resin for-
mulation determines such properties as strength, fuel,
chemical properties, swelling resistance, and perme-
ability. The formulation should not reduce the poros-
ity or filtering ability of the filter. Typically, the
phenolic resin is the novolac type, and the resin con-
tent is about 20% to 30%. In the making of filter
paper, the resin impregnation rate and cure tempera-
tures are controlled to achieve partial cure. The pre-
impregnated substrate (paper) is cut to size and
folded. The partially cured, folded pre-impregnate is
completely cured in an oven at about 180°C.
Bursting pressure for filters is about 30 to 45 psi.
Battery separators are used mainly for the sepa-
ration and electrical insulation of the electrodes in
automobile batteries. Separators are either paper or
sintered polyvinyl chloride (PVC) or polyethylene
fiber sheet-based. Impregnation is via low-molecu-
lar-weight, alkaline-catalyst-cured (resole) phenolic
resin. The impregnated substrate is corrugated to
form ribs and then cut to a size of about 0.0018 to
0.006 m. Typical characteristics of separators are
porosity (to allow current flow) and high oxidation
resistance.
Phenolic Resins in Molding
Applications
About 160 to 165 million pounds of phenolic
resins are used annually in molded parts and
2: PHENOL
FORMALDEHYDES 33

products, accounting for about 5.5% of the total the caliper inside diameter over a wider tempera-
phenolic resins market. Though they represent a ture range (Figures 2.4 to 2.11).
relatively small part of the phenolic resins market, Current trends in phenolic resins consumption
phenolic molding compounds are used in many include the use of phenolic resins in rubber com-
applications, such as in appliances, closures, electri- pounding and tackifying applications, and in struc-
cal, housewares, and transportation industries. This tural composites. Occidental Chemical Durez
versatility is due to their ease of molding into intri- Division, among others, produces four types of rub-
cate parts and products and their inherent dimen- ber modifying phenolic resins:
sional stability and accuracy.
The appliances, closures, and housewares indus- 1. Thermoplastic phenolic tackifiers and proces-
tries prefer the use of resole-based phenolic mold- sing aids.
ing compounds in the making of household-type 2. Phenolic reinforcing resins.
products because (unlike novolacs which give off
ammonia) resoles give off water upon curing and 3. Phenolic reinforcing and tackifying resins.
are odor free. Some of the numerous resole-based 4. Phenolic resins for bonding rubber compounds
applications are bottle caps, knobs, utensil handles, to fabric.
stovetops, toaster components, refrigerator switch
boxes, hermetically sealed switches, steam irons,
and sterilizable hospital equipment. The absence of
ammonia prevents the problem of corrosion from
nitrous acids that could be produced by the pres-
ence of an electric arc in switches.
The two-stage novolac-based phenolic molding
compounds are more dimensionally stable than
resoles and are used for high strength and non-
household applications.
Owing to their shock resistance, impact grades
of phenolic molding compounds are used for auto-
motive and industrial pulleys, electrical switch
gears and switch blocks, fuse holders, and motor Figure 2.4 Occidental Chemical Corporation, Durez
housings and frames. Division, phenolic resins in under-the-hood,
Electrical grades of phenolic molding com- automotive applications. (Courtesy of Occidental
pounds, because of their high dielectric strength, Chemical Corporation.)
are used for automotive ignition parts (distributor
caps, coil tops, and rotors), wiring device parts, cir-
cuit breakers, commutators (unidirectional current
devices connected to the electric motor or genera-
tor), brush holders, and electronic connectors.
Heat-resistant grades are used for appliance ther-
mal barriers such as stovetops, thermostat bases, auto-
motive ashtrays, switch cases, and terminal blocks.
Other under-the-hood automotive applications of
phenolic molding compounds are resistant to auto-
motive fluids, gasoline, coolants, lubricants, and
salt solutions. These include disc brake caliper pis-
tons, thermostat housings, water pumps, water
pump impellers, throttle bodies, pulleys, rocker arm
covers (engine block covers), and solenoids. The
disc brake caliper piston needs to have a low coef- Figure 2.5 Thermostat housing of an automobile
ficient of thermal expansion to help maintain the engine made from phenolic resins. (Courtesy of
relative fit between the piston outside diameter and Occidental Chemical Corporation.)
34
Figure 2.6 Throttle body of an automobile engine
made of phenolic resins. (Courtesy of Occidental
Chemical Corporation.)
Figure 2.7 Water pump of an automobile engine
made from phenolic resins. (Courtesy of Occidental
Chemical Corporation.)
Some of Durez’s products include tires, drive
belts, shoe and boot soles, rubber hoses, and rubber
gaskets.
American Cyanamid Company produces modi-
fied, toughened phenolic resins for glass fiber, ara-
mid fiber (Kevlar, Nomex), and graphite composites
suitable for aircraft interior and ablative applica-
tions. Moderate tack and drape, excellent flame
resistance, low smoke generation, non-toxicity, and
high temperature resistance are typical characteris-
tics of these resins. American Cyanamid’s modified
phenolic resin suitable for nylon and aramid com-
posite helmets has high toughness and ballistic
impact resistance.
HANDBOOK OF THERMOSET PLASTICS
Figure 2.8 Water pump impeller made from
phenolic resins. (Courtesy of Occidental Chemical
Corporation.)
Figure 2.9 Rocker arm cover of an automobile
engine made from phenolic resins. (Courtesy of
Occidental Chemical Corporation.)
The nose cone on the large external fuel tank
that supplies fuel (liquid hydrogen and oxygen) to
the space shuttle main engine is made of phenolic
resin/carbon fiber composite. The nose cone pro-
tects the system from thermal failure because it can
withstand temperatures up to 1000°F (537.8°C) and
loads up to 50 g mass during its 8.5 minutes of crit-
ical operation. (The nose cone, previously made of
metal with a protective foam coating, is produced
for NASA by Martin Marietta Manned Space
Systems, New Orleans LA.) The phenolic resin/car-
bon fiber composite (prepregnate) used in the nose
cone was supplied by Cytec Industries, West
Peterson, NJ [49].
2: PHENOL
FORMALDEHYDES
Figure 2.10 A one-step phenolic molding
compound from Rogers Corp. was selected for lead
insulation in these audio cable connectors for
Switchcraftt. The compound resists creep and has
excellent electrical properties. (Courtesy of the
Rogers Corporation.)
Figure 2.11 Variety of phenolic resins-based
(paper, linen, canvas) laminate chips compared to
light-colored epoxy-glass laminate chips. The
comparable mechanical and electrical insulation
properties, but lower costs of the phenolic
laminates, make them choice materials. (Courtesy
of Accurate Plastics, Inc.)
Phenolic Resins in Coating
Applications [2,4,50]
The very good properties and characteristics that
make phenolic resins good adhesives and molding
compounds also make them a very good protective,
environmental, high temperature, and anti-corrosion
coating for a variety of materials, such as alumi-
num, bronze, iron, and magnesium.
Phenolic coating resins have good wetting and
adhesive properties, and very good chemical and
abrasion resistance. The baking step in coating
35
production involves a cross-linking process. Cross-
linking makes the coating insoluble, strong, and
resistant to exposure to chemicals, solvents (except
alkalis), and hot water. It also makes phenolic coat-
ing resins tasteless and odorless.
Phenolic coating resins are good electrical insu-
lators. Dielectric strength for these resins is about
500 V/mm; dissipation factor and water absorption
are very low. They also have good thermal resis-
tance with a continuous-use temperature of 145°C
and can withstand high temperatures up to 350°C
for short periods. Phenolic coating resins exhibit
flexibility and compatibility with other resins, such
as polyurethanes, epoxies, alkyds, and polyvinyl
butyryl, and can be easily modified to suit various
applications. Also, phenolic resins are sterilizable
and can be used for food applications where
sterilization is a Food and Drug Administration
requirement.
Major coating applications are as protective coat-
ings, undercoats, and primers for automotives;
metal containers and pipes; and industrial equip-
ment. Examples of specific applications of phenolic
resins, such as coatings, are in heat exchangers,
pipelines, boiler pipes, reaction vessels, storage
tanks, brine tanks, solvent containers, food contain-
ers, railroad cars, beer and wine tanks, beer cans,
pail and drum linings, water cans, rotors, blower
fans and ducts in heating and air conditioning sys-
tems, boats, ships, wood finishes, and paper.
Because of their versatility phenolic coating
resins can be applied by most available coating
technologies, such as dip and spray (pneumatic and
electrostatic) coating in solutions, high solids, and
powder forms. Georgia Pacific Resins, Inc. and
other plastics companies offer a variety of grades
of coating resins. A particular coating application
can have more than one resin type; for example, a
rail car could have an epoxy primer, a modified
phenolic undercoat, and a polyurethane finish.
Modification of Phenolic Resins
Post-addition of Urea
Addition of urea to a phenolic resin is today the
current commercial practice. There are different
levels of addition and they cause several effects:
• Decrease of the content of free formaldehyde.
• Decrease of the viscosity of the adhesive.
36
• Acceleration of the hardening reaction via the
higher possible degree of condensation of the
resin at the same viscosity.
• Reduction of resin costs.
The urea usually is added to the finished PF-
resin and causes a distinct decrease of the viscos-
ity due to cleaveage of hydrogen bondings [51]
and due to the dilution effect. There is obviously
no co-condensation of this post-added urea with
the phenolic resin. Some co-condensation has
been shown to occur during hot-pressing. Urea
only reacts with the free formaldehyde of the
resin forming methylols, which do not react fur-
ther due to the high pH. At higher temperatures
during hot-pressing, some phenol-urea co-conden-
sation can occur [48,52,53].
The higher the amount of post-added urea, the
worse are the properties of the boards. A reason
for this might be the diluting effect of urea on the
PF-resin. Amelioration of the co-condensation pro-
cess also could help in the optimization of the
urea addition. In this respect one can explain the
apparently surprising results of Oldörp and
Marutzky [54], who have found better board prop-
erties with increased urea post-addition, a clear
indication that some co-condensation has indeed
occurred.
Co-Condensation Between Phenol
and Urea
Real co-condensation between phenol and urea
can be performed in a number of different ways:
• Reaction of methylol phenols with urea [55
58].
• Reaction of UFC (urea
formaldehyde

concentrate) with phenol under acid conditions
followed by an alkaline reaction [59,60].
• Alkaline co-condensation to yield commercial
resins and the products of reaction obtained
thereof [52,61]. The kinetics of the co-
condensation of monomethylol phenols and
urea [62,63] have also been reported.
Model reactions proving urea
phenol

formaldehyde co-condensation are described both
by Tomita and Hse [55,59,64] and by Pizzi et al.
[52,61,62].
HANDBOOK OF THERMOSET PLASTICS
Addition of Tannins, Lignin, and
Isocyanates
Purposes of the addition of tannins are:
• Acceleration of the hardening reaction [65,66],
unsuccessful with hydrolyzable chestnut tan-
nins [65], but successful when using polyfla-
vonoid tannins [66].
• Replacement of phenol or part of the PF-resin
[67
69].
The addition of lignins to phenolic resins can be
(i) as an extender (e.g. in order to increase the cold
tack or to reduce costs), or (ii) in order of a chemi-
cal modification of the resin, whereby the lignin is
chemically incorporated into the phenolic resin.
The basic idea behind this is based on the chemical
similarity between the phenolic resin and lignin, or
between phenol and the phenylpropane unit of the
lignin. The lignin can be added at the beginning,
during the cooking procedure, or at the end of the
condensation reaction (with a following reaction
step between the lignin and the phenolic resin). It is
not fully clear if the lignin really is incorporated
into the phenolic resin or not. In practice, lignin is
at the moment used, if at all, only as a more or less
neutral filler in glue resins, without adding any spe-
cial advantage (sometimes even not in terms of
costs).
The use of isocyanate as a fortifier for phenolic
resins was not thought to be worthwhile. Deppe
and Ernst [70] had reported a precurring
and
hence a negative effect reaction between the isocy-
anate and the phenolic resin
even if both compo-
nents had been applied separately to the particles.
However, extensive industrial application of pre-
mixed glue-mikes of isocyanate and phenolic resin
in water to bond wood panel products have been
shown to yield excellent bonding results [71
73],
to yield copolymers linked by urethane bridges dur-
ing curing of the wood panel in the hot press. The
reactions involved and their reasons for occurring
have also been clarified and presented [71]. Hse
et al. [74] have described a similar system, but with
the isocyanate and the phenolic resins added sepa-
rately to the wood. This also yielded some good
results, but not as good as the former system due to
the decreased mobility and diffusion hindrance
induced impossibility to maximize reaction in situ
2: PHENOL
FORMALDEHYDES
between the two resins. These resins are now com-
mercial in both the emulsified isocyanate/PF form,
hence as single component adhesives, and in being
composed directly in the glue mix, just before
application by mixing PF resin and non-
emulsifiable isocyanate [71,72,75].
Resorcinol Adhesives
Resorcinol
formaldehyde (RF) and phenol

resorcinol
formaldehyde (PRF) cold-setting adhe-
sives are used primarily in the manufacture of
structural, exterior-grade glulam, finger joints, and
other exterior timber structures. They produce
bonds not only of high strength, but also of out-
standing water and weather resistance when
exposed to many climatic conditions [8,76,77]. PRF
resins are prepared mainly by grafting resorcinol
onto the active methylol groups of low-
condensation resoles obtained by the reaction of
phenol with formaldehyde. Resorcinol is the chemi-
cal species that gives these adhesives their charac-
teristic cold-setting behavior. At ambient
temperature and on addition of a hardener, it pro-
vides accelerated and improved cross-linking not
only to resorcinol
formaldehyde resins but also to
the phenol
formaldehyde resins onto which resor-
cinol has been grafted by chemical reaction during
resin manufacture. Resorcinol is an expensive
chemical, produced in very few locations around
the world (to date only three commercial plants are
known to be operative in the United States,
Germany, and Japan), and its high price is the
determining factor in the cost of RF and PRF adhe-
sives. It is for this reason that the history of RF and
PRF resins is closely interwoven, by necessity, with
the search for a decrease in their resorcinol content,
without loss of adhesive performance. Today less
than 1% of the resorcinol resins used commercially
for wood are pure RF resins, and this amount is
decreasing fast as the comparatively less expensive
PRF resins are now so well engineered as to often
outperform even the best pure RF resins. However,
about 7 to 8% of the total resorcinol resins pro-
duced, namely the portion used for tire cord bin-
ders, are still pure RF resins.
In the past decades, significant reductions in res-
orcinol content have been achieved: from pure
resorcinol
formaldehyde resins, to PRF resins in
which phenol and resorcinol were used in equal or
37
comparable amounts, to the modern-day commer-
cial resins for glulam and finger jointing in which
the percentage, by mass, of resorcinol on liquid
resin is on the order of 16 to 18%. A step forward
has also been the development and commercializa-
tion of the “honeymoon” fast-set system [8,78],
coupled with the use of tannin extracts, which in
certain countries are used to obtain PRFs of 8 to
9% resorcinol content without loss of performance
and also provide some other advantages (such as
gluing of high moisture content timber). This was a
system improvement, not an advance on the basic
formulation of PRF resins.
Chemistry of RF Resins
The same chemical mechanisms and driving
forces presented for phenol
formaldehyde resins
apply to resorcinol resins. Resorcinol reacts readily
with formaldehyde to produce resins which harden
at ambient temperatures if formaldehyde is added.
The initial condensation reaction in which A-stage
liquid resins are formed leads to the formation of
linear condensates only when the resorcinol/formal-
dehyde molar ratio is approximately 1:1 [79]. This
reflects the reactivity of the two main reactive sites
(positions 4 and 6) of resorcinol [80]. However,
reaction with the remaining reactive, but sterically
hindered, site (2-position) between the hydroxyl
functional groups also occurs [79]. In relation to
the weights of resorcinol
formaldehyde conden-
sates which are isolated and on a molar basis, the
proportion of 4- plus 6-linkages relative to 2-
linkages is 10.5:1. However, note must be taken of
the fact that the first mentioned pair represents two
condensation sites relative to one. The difference in
reactivity of the two types of sites (i.e. 4- or 6-
position relative to the 2-position) is then 5:1 [79].
Linear components always appear to form in prefer-
ence to branched components in A-stage resins
[79], that is, terminal attack leads to the preferential
formation of linear rather than branched conden-
sates. This fact can be attributed to:
1. The presence of two reactive nucleophilic
centers on the terminal units, as opposed to
single centers of doubly bound units already
in the chain.
2. The greater steric hindrance of the available
nucleophilic center (nearly always at the
38
HO
HO *2 OH
1 3 HCHO
6 4
* 5 *
Scheme 2.6
2-position) of the doubly bound units, as
opposed to the lower steric hindrance of at
least one of the nucleophilic centers of the
terminal units (a 4- or 6-position always
available). The former is less reactive as a
result of the increased steric hindrance. The
latter are more reactive.
3. The lower mobility of doubly bound units,
which further limits their availability for reac-
tion and hence severely limits their contribution
to final, hardened cross-linking (Scheme 2.6).
It is then these units, and for these reasons, that
they can be substituted with the much cheaper
phenol in PRF resins.
The absence of methylol (aCH2OH) groups in
all six lower-molecular-weight resorcinol formalde-
hyde condensates which have been isolated [79]
reflects the high reactivity of resorcinol under acid
or alkaline conditions (Scheme 2.6). It also shows
the instability of its para-hydroxybenzyl alcohol
groups and their rapid conversion to para-hydroxy-
benzyl carbonium ions or quinone methides. This
explains how identical condensation products are
obtained under acid or alkaline reaction conditions
[79]. In acid reaction conditions methylene ether-
linked condensates are also formed, but they are
highly unstable and decompose to form
stable methylene links in 15 minutes to 1 hour at
ambient temperature [81,82]. From a kinetic point
of view, the initial reaction of condensation to form
dimers is much faster than the subsequent conden-
sation of these dimers and higher polymers.
The condensation reaction of resorcinol with form-
aldehyde on an equal molar basis and under identical
conditions also proceeds at a rate that is approxi-
mately 10 to 15 times faster than that of the equiva-
lent phenol
formaldehyde system [8,83]. The high
reactivity of the resorcinol
formaldehyde system
renders it impossible to have these adhesives in resol
form. Therefore, only resorcinol
formaldehyde
HANDBOOK OF THERMOSET PLASTICS
OH HO OH
CH2 CH2 CH2
CH2
HO OH HO OH
novolacs, thus resins not containing methylol groups,
can be produced. All the resorcinol nuclei are linked
together through methylene bridges with no methylol
groups present, and generally without any presence
of methylene
ether bridges either.
The reaction rate of resorcinol with formalde-
hyde is dependent on the molar ratio of the two
constituents, the concentration of the solution, pH,
temperature, the presence of various catalysts, and
the amount of certain types of alcohols present
[31,32,84,85]. The effect of pH and temperature on
the reactivity and gel time of the resorcinol

formaldehyde system presents the same trend as for
all phenolic
formaldehyde reactions, with a mini-
mum of reactivity at around pH 4 and with the rate
of reaction becoming rapidly faster at progressively
more alkaline and more acidic pH values [32,33].
Methanol and ethanol slow down the rate of reac-
tion. Other alcohols behave similarly, the extent of
their effect being dependent on their structure.
Methanol lengthens gel time more than that of
other alcohols; higher alcohols being less effective.
The retarding effect on the reaction is due to tem-
porary formation of hemiacetals between the meth-
anol (or other alcohols) and the formaldehyde. This
reduces the reaction rate because of the lower con-
centration of available formaldehyde [31,85]. Other
solvents also affect the rate of reaction by forming
complexes or by hydrogen bonding with the resor-
cinol [33,85].
In the manufacture of pure resorcinol resins, the
reaction would be violently exothermic unless con-
trolled by the addition of alcohols (Scheme 2.6).
Because the alcohols perform other useful functions
in the glue mix, they are left in the liquid glue.
PRF adhesives are generally prepared first by reac-
tion of phenol with formaldehyde to form a PF
resole polymer, that has been proved to be in the
greatest percentage, and often completely, linear
[79] (Scheme 2.7).
In the reaction that follows, the resorcinol chem-
ical is added in excess, in a suitable manner, to
2: PHENOL
FORMALDEHYDES
OH
+ HCHO
OH
HO
Scheme 2.7
react with the
CH2OH groups of the already pre-
pared PF resole to form PRF polymers in which the
terminal resorcinol groups can be the resorcinol
chemical or any type of resorcinol
formaldehyde
polymer (Scheme 2.7).
Where resorcinol adhesives are not suitable,
resins can be prepared from modified resorcinol
[33]. Characteristics of these types of resins are
those used for tire cord adhesives, in which a pure
resorcinol
formaldehyde resin is used, or alterna-
tively, alkyl resorcinol, or oil-soluble resins
suitable for rubber compounding are obtained by
pre-reaction of resorcinol with fatty acids in the
presence of sulfuric acid at high temperature fol-
lowed by reaction with formaldehyde. Worldwide
more than 90% of resorcinol adhesives are used as
cold-setting wood adhesives. Their other most
notable application is as tire cord adhesives, which
constitutes about 5% of the total worldwide use of
resorcinol.
Phenol
Resorcinol

Formaldehyde Adhesives
PRF adhesives in which a liquid phe-
nol
resorcinol
formaldehyde adhesive and a pow-
der or liquid hardener are used are currently the
most commonly used in industry. Pure resorcinol

formaldehyde (RF) adhesives were used extensively
up to a few years ago. They fell into disfavor
because of the high price of the resorcinol chemical
needed to make them. They are still used industri-
ally when particularly difficult wood-gluing
39
OH
HO H2C CH2OH
n
OH
+
OH
OH OH
H2C CH2
OH
n
problems arise. PRF adhesives in which a liquid
phenol
resorcinol
formaldehyde adhesive and a
liquid hardener are used quite extensively in
Europe, as they have several handling advantages
for this market. These adhesives are mixed before
use in a mass/mass ratio of liquid adhesive resin
(50 to 60% solid content) to powder hardener of
5:1, or when using a liquid hardener of 4:1, 2:1, or
even 1:1 (depending on the type). The powder
hardener is generally a mixture of equal parts para-
formaldehyde fine powder and fillers, these latter
being comprised of 200-mesh wood flour or a mix-
ture of wood flour and nutshell flour (also 200
mesh). Adhesive types presenting a liquid hardener
use as hardener formaldehyde, formurea, and when
needed (to avoid undue formaldehyde smell) also
oxazolidine as hardener.
All properly formulated resorcinol-based adhe-
sives must have a viscosity low enough in
aqueous
alcoholic solutions to flow with ease into
all the interstices of the wood surface. Wetting abil-
ity is promoted by the alcohol. The paraformalde-
hyde (polyoxymethylene) used as hardener in
powder hardener types is an addition polymer
composed of a few to over 100 formaldehyde
monomers. It dissolves slowly in water by depo-
lymerization to formaldehyde monomers. The rate
of depolymerization depends on the degree of poly-
merization of the paraformaldehyde, the size of the
particles, and the pH. Therefore, the working life or
pot life of a glue mix can be adjusted by selecting
the type of paraformaldehyde and the pH correctly,
as its success also depends on the rate of supply of
40
formaldehyde monomer. Fillers are added to give
consistency to the glue mix, to control viscosity
and thixotropic characteristics, to form a fibrous
reinforcement of the adhesive film, and to lessen
the cost. Wood flour is used as a filler to obtain
better gap filling where rough or uneven surfaces
must be bonded, or where low bonding pressures
must be used. Nutshell flours, such as coconut shell
flour, walnut shell flour, peach pit shell flour,
macadamia nut shell flour, or even olive stone flour
are used as fillers to lower absorptive qualities and
to provide smooth-flowing mixtures. Inorganic fil-
lers are also used especially in Europe, although
this is a practice to avoid as it blunts too readily
the saws used to cut the finished bonded product.
Clays and silica smokes can also be used in very
small amounts to control the thixotropic consis-
tency of the glue mix.
As the formaldehyde reacts with the resorcinol-
based resin, condensation, cross-linking, and net-
working occurs exclusively through the resorcinol
reactive sites (phenol does not participate in the
hardening reaction), with the formation of high-
molecular-weight polymers. There is considerable
secondary forces interaction between the growing
resorcinol polymers and the noncrystalline hemicel-
lulosic and lignocellulosic molecules of the sub-
strate. The growing adhesive polymers continue to
interact to form colloidal particles and then a gelati-
nous film. This mechanism depends strongly on the
moisture content of the wood, which determines the
rate of water and solvent absorption.
The advantage of ambient-temperature curing is
that the moisture escapes gradually from the hard
film formed on curing, inducing a minimum of resid-
ual stresses on the joint and allowing the glue-line to
assume the aspect of a molecularly porous solid. As a
consequence, the hard film is able to transpire in the
same way as wood, which minimizes checking or
crazing and allows the glued joint to survive exposure
to the extremes of humidity cyc1es.
Special Adhesives of Reduced
Resorcinol Content
Together with the more traditional finger jointing
adhesives that have just been discussed, a series
of ambient-temperature, fast-setting, separate applica-
tion systems have also been developed. These
eliminate the long delays caused by the use of
more conventional phenol
resorcinol
formaldehyde
HANDBOOK OF THERMOSET PLASTICS
adhesives that require lengthier periods to set. These
types of resorcinol adhesives are applied separately.
They were first developed in the United States
[34
37] to bond large components where presses
were impractical. Originally these separate applica-
tion or “honeymoon” systems were described as
follows: “Component A is a slow-reacting phenol

resorcinol
formaldehyde resin with a reactive hard-
ener. Component B is a fast-reacting resin with a
slow-reacting hardener. When A and B are mated,
the reactive parts of the component react within min-
utes to form a joint which can be handled and pro-
cessed further.” [37]. Full curing of the slow-reacting
part of the system takes place with time. The m-ami-
nophenol used for component B is a frightfully
expensive chemical, and for this reason these sys-
tems, in the form they were originally conceived,
were discarded and not used industrially [37,78]. In
their original concept component A is a traditional
phenol
resorcinol
formaldehyde cold-setting adhe-
sive at its standard pH of between 8 and 8.5 to
which formaldehyde hardener has been added. Flour
fillers may be added or omitted from the glue
mix. Component B is a phenol
m-aminophenol

formaldehyde resin with a very high pH (and there-
fore a high reactivity), which contains no hardener or
only a very slow hardener.
More recently, modification of these systems
has been used extensively in industry with good
success. Part A of the adhesive is again a standard
phenol
resorcinol
formaldehyde (PRF) cold-
setting adhesive with powder hardener added at its
standard pH. Part B can be either the same PRF
adhesive with no hardener and the pH adjusted to
12, or a 50 to 55% tannin extract solution at a pH
of 12 to 13, provided that the tannin is of the con-
densed or flavonoid type, such as mimosa, quebra-
cho, or pine bark extract, with no hardener
[38
40,78]. The results obtained with these two
systems are good, and the resin not only has all the
advantages desired but also as a result of the use of
vegetable tannins and of the halving of the resor-
cinol content of the entire adhesive system, is con-
siderably cheaper [38
40,78]. These variants of the
original concept have now been in commercial use
for more than twenty years. These variants, due to
their high rate of curing, are also excellent for
bonding wet/green timber [41,42].
The adhesive works in the following manner.
Once the component A glue mix is spread on one
finger joint profile and component B on the other
2: PHENOL
FORMALDEHYDES
finger joint profile and the two profiles are joined
under pressure, the reaction of component B with
the hardener of part A is very fast. In 30 minutes at
25°C finger joints prepared with these adhesives
generally reach the levels of strength that finger
joints glued with, more conventional phenolic adhe-
sives are able to reach only after 6 hours at 40 to
50°C or in 16 to 24 hours at 25°C [39,78]. Clamping
of laminated beams (glulam) bonded with these
fast-set honeymoon adhesives is on average only 3
hours at ambient temperature compared with the 16
to 24 hours necessary with traditional PRF resins
[38
40]. These adhesives also present two other
advantages, namely: (i) The capability to bond with-
out any decrease of performance at temperatures
down to 5°C, and (ii) They are able to bond “green”
timber at high moisture content, a feat which is used
in industrial glulam bonding since their commercial
introduction in 1981 [38,41,42].
A second variant to honeymoon separate applica-
tion adhesives that reached commercialization has
been to use PRF adhesive on a profile and a solu-
tion containing a dilute ammonia solution on the
other profile [43]. This system, which is also in
commercial use, presents in some markets such as
Europe some acceptance problems due to the objec-
tionable ammonia emission from the glue-mix. It
has the disadvantage in relation to the previous one
that the percentage of resorcinol in the total resin
system is not markedly decreased.
Honeymoon separate application adhesives of
comparable performance but based on MUF resins
also exist and have now been commercial in Europe
for sometime [44,45]. They use a MUF resin on one
joint profile and a mix of a very diluted organic acid
plus a thickener on the other profile. Branched, tra-
ditional type PRF resins also exist, the so-called
“blue glues” from the characteristic color of some of
them, in which branching is the method used to
halve the resorcinol content of the adhesive [40,86].
These are a true resin formulation advances on tradi-
tional adhesives, while the honeymoon types are
systems rather than resin advances.
Thermosetting Phenolic
Adhesives Based on Natural
Resources
Phenolic bio-based adhesives have been under
investigation for many years. The use and application
41
of adhesives based on natural and renewable poly-
phenolic materials by industry and the general
public is often thought of as a new approach that
requires novel technologies and methods to imple-
ment. Processes based on the chemical modification
of natural products offer opportunities for produc-
ing a new generation of high performance, high
quality products. The distinct advantages in the
utilization of natural materials (e.g. lower toxicity,
biodegradability, and availability) need to be paral-
leled by more efficient and lower cost methods of
production. Extensive reviews of these adhesives,
some of them such as those based on condensed
vegetable tannins used commercially for a long
time, already exist, and the reader is directed to
these for accurate in depth information [8,87,88].
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Clarke MR, Steiner PR, Anderson AW. USP
1988;4(824):896.
Haupt RA, Sellers Jr. T. Ind EngChem Res 1994;
33:693
7.
Lu X, Pizzi A. Holz Roh Werkstoff 1998;56:
339
46.
Pizzi A, Garcia R, Wang S. J Appl Polymer Sci
1997;66:255
66.
Pizzi A, Mtsweni B, Parsons W. JApplPolymer Sci
1994;52:1847
56.
Pizzi A, Stephanou A. J Appl Polymer Sci 1993;49:
2157
70.
Pizzi A, Stephanou A. Holzforschung 1994;48:
35
40.
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