International Journal of Adhesion & Adhesives 70 (2016) 102–109

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International Journal of Adhesion & Adhesives

journal homepage: www.elsevier.com/locate/ijadhadh

Innovation in poly(vinyl acetate) water resistant D3 glues used

in wood industry
Fabio Chiozza a, Benedetto Pizzo b,n
a
Vinavil S.p.A, via Toce, 7, Villadossola, VB, Italy
b
CNR-IVALSA, Istituto per la valorizzazione del legno e delle specie arboree (Trees and timber Institute), via Madonna del Piano, 10, I-50019, Sesto Fiorentino,
FI, Italy

art ic l e i nf o a b s t r a c t

Article history: Poly(vinyl acetate) (PVAc) water-resistant glues used in the wood industry and belonging to the class of
Accepted 6 June 2016 durability D3 show high resistance to both water and heat compared to the usual PVAc-based ther-
Available online 11 June 2016 moplastic products. In conventionally synthesised adhesives this is attained by means of cross-linking
Keywords: (although limited) of the linear polymer chains and moreover by using inorganic salts, such as alumi-
Adhesives for wood nium chloride.
Latex and dispersion The paper illustrates the limits of these products and presents the prospects in the chemistry of
Water based industrial-grade D3-class PVAc adhesives. More in detail, it is shown how the individual roles of both
Environmental issues cross-linking agent and aluminium chloride contribute to the occurrence of recurring inconveniences
Aluminium chloride
characterising conventional PVAc-D3 glues, which include formaldehyde release during time (mostly
related to the curing agent), glueline colouring and indirect staining of wood (both are mostly evident in
selected wood species, in the presence of either heat or UV irradiation), acidic pH, and equipment cor-
rosion (related to the presence of aluminium chloride).
Understanding those mechanisms has constituted the basis for the development of newly synthe-
sised PVAc-D3 glues, whose characterisation is expressly reported in the present work. Such systems
have shown good adhesion to wood surfaces and have exhibited neither corrosive nor chromatic
alteration evidences, as well as absence of formaldehyde emissions. All these occurrences were verified
by specific tests, such as corrosion on steel, measurements of the formaldehyde content of the dispersion,
and emissions from panel boards, and glueline exposure to both temperature and UV irradiation after
application in selected wood species.
& 2016 Elsevier Ltd. All rights reserved.

1. Introduction applied as water-based dispersions, and therefore surfactants,

The types of adhesives commonly used in the wood industry
for furniture applications can be both thermosetting and ther-
moplastic in nature, and the choice on which type of product
should be specifically used, depends on different criteria such as:
final use, required performances, costs, application process,
environmental issues etc. Water based poly(vinyl acetate) (PVAc)
dispersions are the most used among the thermoplastic polymers
as the basis for glues to be used with wood and wood products [1].
From a chemical-physical standpoint, these adhesives are
affected by both temperature changes and water. As regards
temperature, this dependence is a common characteristic of
thermoplastic polymers. Instead, the water dependence in PVAc
wood adhesives is related to the fact that these products are
n
Corresponding author.
E-mail addresses: f.chiozza@vinavil.it (F. Chiozza), pizzo@ivalsa.cnr.it (B. Pizzo).
colloid protectors and other hydrophilic compounds are present in
formulations [2], thus increasing the water affinity of the disper-
sion compared to the original pure polymer. On the other hand,
water-based PVAc dispersions are free of any low boiling tem-
perature organic solvent, which implies limited VOC emissions.
Considering that these products have been stably introduced
into the market since the 1950s, a well-established standardisation
system has been developed, and two European norms exist pro-
viding the criteria to be followed for their classification [3] and for
establishing the procedures to be applied to evaluate the related
performances [4]. EN 204 [3] classifies non-structural adhesives
(like PVAc) in four different durability classes, and each class is
associated with an example of climatic conditions and fields of
application. Among them, products belonging to D3 class are
highly interesting because they show performances similar to
thermosetting products used for non-structural applications, such
as urea-formaldehyde (UF) resins, but they are monocomponent
and are able to set at room temperature (the so-called “cold

http://dx.doi.org/10.1016/j.ijadhadh.2016.06.003
0143-7496/& 2016 Elsevier Ltd. All rights reserved.
 F. Chiozza, B. Pizzo / International Journal of Adhesion & Adhesives 70 (2016) 102–109
setting”) in a reasonable time. Therefore, the expression “D3
glues”, largely used in the practice, refers to adhesives belonging
to the D3 class which have been subjected to the conditioning
sequence number 3 (D3-3) specified in [3]. In detail, this durability
class refers to both:
– interior use with frequent short-term exposure to running or
condensed water and/or to heavy exposure to high humidity;
– exteriors not exposed to weather.
On the other hand, it is also known [5] that the reliability of D3-
type glues used to prepare wood assemblies is not only related to
“water resistance” but rather to a combination of different
characteristics:
– water resistance, as mentioned,
– resistance to heat,
– good resistance to sustained loads (creep resistance).
All these properties are also regulated by specific standards.
Usually PVAc glues are not capable of reaching all the above-
mentioned requirements to be reliably classified in the durability
class D3 and instead they are normally classified in the less per-
forming classes D1 and D2. However, it is also possible for PVAc
dispersions to meet the requirements of class D3 by introducing a
suitable cross-linker into the molecule during the polymerisation
phase [6–8], and this class of products is nowadays considered as
“conventional D3 PVAc glues” (the chemistry of these products
will be better described in Section 2). This possibility has opened
up this class of products to a plethora of different applications. In
fact, in the industry D3 glues are widely applied in:
– furniture manufacture, including veneering of wood and deri-
vates, plank joints, block gluing, lamination with hot-melts
(HPL) or continuous press (CPL), thermo lamination of timber
products with decorative films;
– furniture designated for wet conditions, including baths, kitch-
ens, garden furniture, outdoor tools;
– window and door manufacture, including lamination of window
frames and window corner joints, mortise-tenon joints;
– installation of parquet and laminate floors, including tongue and
groove, sealing of joints;
– manufacture of laminate floors.
However, the use of conventional D3 glues can induce some
recurrent inconveniences to face, such as formaldehyde release
during time, glueline colouring, acidic pH, indirect staining of
wood and equipment corrosion [9,10]. Formaldehyde emission is
mainly an issue in the wood bonding industry due to the binders
used for the production of composites such as plywood, particle-
board, and medium density fibreboard, and it is mostly related to
the hydrolysis of urea-formaldehyde based adhesives [11],
although the emission of free-formaldehyde is also possible.
However, formaldehyde can be also moderately emitted from
conventional D3 PVAc glues, due to curing reactions involving a
polymer latex [12,13]. This occurrence makes these products at
risk due to the newest and strictest requirements provided in
more recent environmental policies, also involving the sector of
wood-based products. For instance, Germany and France have
already provided specific regulations concerning indoor emissions
of products for the building industry (including furniture and
floorings), and also Belgium is adopting similar rules. In fact,
beyond national legislation, key international buyers in composite
wood products and furniture are forcing strict limits in terms of
formaldehyde emissions [14].
103
Another peculiar behaviour of D3 PVAc glues is the chromatic
alteration of the bondline during time, which could represent an
aesthetic defect for some specific products (panels, furniture etc.).
Among the several factors affecting this phenomenon, it is known
that light exposure, temperature and the nature of the wood
species employed are the most important ones [10]. Several
references in the literature have provided evidence of chromatic
alteration of the PVAc glue line exposed to temperature and light
over time [9,15]. In fact these external conditions give to the dis-
persion film the needed energy for the development of chemical
reactions producing chromophore compounds. Hydrolysis reac-
tions of some ester groups and the consequent acetic acid for-
mation as well as the generation of oxidation compounds such as
carbonylic groups linked to unsaturated groups are considered as
the main origin of the yellowing and brownish colours of the glue
line exposed to temperature and light over time [16]. Conversely it
is quite difficult to explain chromatic alteration of the glue line
with different wood substrates when exposed to the same envir-
onmental conditions. Temperature and light both affect in differ-
ent ways wood species and polymers, and the final chromatic
effect could be considered as a resultant of these two different
systems (glue-wood). Specific references in the literature [17] have
indicated that, in the case of cherry wood, both luteolin and nar-
ingenin (detected by means of GC–MS analysis carried out on the
substances extracted from thin slices of that wood) are generated
after exposure to temperature and UV. These two chemical species
are able to form complexes with amphoteric ions by shifting
absorption towards higher wave numbers, in visible light. There-
fore, an adhesive product containing Al3 þ when applied to cherry
wood, can promote the generation of chromophore compounds.
The use of aluminium salts in conventional D3 PVAc glues also
imply the lowering of the dispersion pH to acidic values, due to the
properties of aluminium compounds to act as Lewis acids. This
occurrence allows the development of the cross-linking reaction
(see Section 2) and in fact any eventual modification of the pH can
compromise adhesive performance. Even, the addition of inorganic
fillers such as calcium carbonate could provoke gas/foam formation
within the glue. The most common salt used in D3 PVAc dispersions
is aluminium chloride, which however introduces chloride ions in
the system. These ions can induce serious corrosion problems with
materials involved in the production, transport, transformation and
application of conventional D3 adhesives. This specific incon-
venience has been mainly put in evidence after the recent intro-
duction in the market of a new generation of substrates (e.g., dec-
orative laminates and impregnated paper) used to laminate wood
derivates, which has forced adhesive suppliers to drive the choice of
the glue from alkaline or neutral products towards D3 adhesives.
Nevertheless, the same steel equipment is usually kept in produc-
tion, and it is usually not manufactured as chloride resistant.
Therefore, the issue of equipment corrosion has arisen.
Although the chemistry of PVAc dispersions is quite well-known
[18], only a few works have been published so far on the chemistry
of D3-class PVAc adhesives of industrial grade [2,8] and, according
to our knowledge, none specifically explains the reasons of the
inconveniences mentioned above. For such a reason, the function of
the various components constituting conventional D3-class poly-
vinyl acetate formulations intended for the wood industry is
described in present paper, together with the role played by these
components in determining such inconveniences. Moreover, the
work also reports on the characterisation of a new industrial for-
mulation that has been synthesised to overcome the described
disadvantages (instead, the synthesis details of the new product are
described elsewhere [19]). The new product has possessed good
adhesion to wood surfaces even when possibly modified with any
inorganic filler, and has exhibited neither corrosive nor chromatic
tendencies as well as an absence of formaldehyde emissions.
104 F. Chiozza, B. Pizzo / International Journal of Adhesion & Adhesives 70 (2016) 102–109

2. Chemistry of conventional D3 PVAc glues for the wood
industry
As mentioned, D3 wood glues mostly used in the wood industry
are poly(vinyl acetate) water based dispersions. The polymer disper-
sion is the result of vinyl acetate polymerisation via a radical process
[20]. Differently from the standard PVAc wood glues (D1 or D2 class
according to [3]), the conventional water-based D3 dispersions contain
an internal cross-linking agent, usually N–methylolacrylamide (NMA).
Fig. 1 shows the reaction mechanism of that cross-linking agent: two
molecules of NMA condense through the hydroxyl-methyl groups, by
leaving one molecule of water to form bis-(acrylamide-methyl)ether
and, in a second step, by releasing one molecule of formaldehyde to
form N,N0 –methylene-bis-acrylamide (Fig. 1). The reaction is affected
by acid catalysis or simply by heat [8]. As soon as the polymer dis-
persion is made, the product is modified by adding an external cross-
linking agent able to act on the protective colloid (usually poly-
vinylalcohol). The choice of this external agent is driven by the need of
lowering the pH of the system (to optimise the NMA reaction
mechanism) and, at the same time, of blocking the hydrophilic action
of the protective colloid (Fig. 2) [2,8]. Furthermore the polymer dis-
persion is modified by means of a coalescing agent (which is usually
constituted by a high boiling temperature solvent) in order to guar-
antee a good film formation process even in critical conditions [18].
However, some products used in water-based D3 PVAc dis-
persions strongly affect their formaldehyde emissions. They are:
– the absence of formaldehyde release during time can be guar-
anteed by excluding the use of NMA as well as of all types of
biocide systems that can generate formaldehyde. Furthermore
particular attention must be placed on the choice of the che-
mical initiators to run the radical polymerisation process;
– the appearance of glue line colouring can be managed by
avoiding the use of aluminium chloride (or of any additive able
to reduce the pH), and of NMA as the internal cross-linking
agent of the polymer. In such a way, the elimination of any
amphoteric metals from the polymer dispersion will limit the
wood staining phenomenon;
– the absence of chlorides and of an acidic pH environment also
excludes any possibility of corrosion.
3. Materials and methods
One conventional latex (A) and one newly synthesised product
(C) were compared. Product C was prepared by an emulsion

– the cross-linking agents used in the polymerisation phase;

– the chemicals initiators also used during the polymerisation;
– the biocide systems added to protect the dispersion from
microbiological pollution.

Fig. 2. Reaction mechanism between the protective colloid and the external cross-
The origin of formaldehyde generated by the cross-linking
linking agent (adapted from [21]).
agent NMA has been already shown in Fig. 1, whereas the reac-
tion scheme producing the release of formaldehyde for the sodium
formaldehyde sulfoxilate/hydrogen peroxide couple (which is a
Fig. 3. Scheme of the reaction between sodium formaldehyde sulfoxilate and
chemical initiator used frequently in the radical polymerisation of hydrogen peroxide producing the release of formaldehyde.
the vinyl acetate monomer) is shown in the scheme in Fig. 3.
Finally, an example of one active principle (1,6–dihydroxy–2,5–
dioxyhexane) commonly used as a biocide system in conventional
water-based dispersion and of its reaction producing for-
maldehyde in acidic conditions is shown in the scheme in Fig. 4.
Based on the analysis of the origin of the inconveniences
mentioned previously and on the chemistry of conventional PVAc
dispersions, some indications of the main characteristics that a
new PVAc product should possess to avoid those same incon- Fig. 4. Reaction scheme of 1,6–dihydroxy–2,5–dioxyhexane that produces for-
veniences are listed below: maldehyde in acidic conditions.

Fig. 1. Cross-linking reaction of PVAc in presence of N –methhylolacrylamide (NMA mechanism).

 F. Chiozza, B. Pizzo / International Journal of Adhesion & Adhesives 70 (2016) 102–109 105

polymerisation batch reaction of poly(vinyl acetate). Furthermore, carried out following the procedure for condition D1 of EN 205 [4]:
it was prepared with the same type and amount of coalescing assemblies were tested after keeping them at 23 °C and 50% r.h. for
agent as for A, in order to obtain a similar minimum film forming 7 days. In this case, EN 204 [3] provides a minimum average
temperature (MFFT). The distinction between adhesives A and C strength of 10 N/mm2. Furthermore, some tests with the shorter
was mostly related to the different polymerisation system: conditioning times of 5 min, 15 min and 30 min were also
carried out.
– formulation A was prepared as a conventional class D3-adhesive Water resistance tests were performed according to condition
of industrial type, that is, also by an emulsion polymerisation D3-3 of EN 205 [4]: after 7 days in normal climate, specimens were
batch reaction of PVAc making use of sodium formaldehyde soaked in water for an additional 4 days and then tested wet. In
sulfoxylate (supplied by Consulchim srl) as the initiator and in this case, EN 204 [3] provides a minimum average strength of 2 N/
presence of a highly hydrolysed, medium molecular weight, poly mm2.
(vinyl alcohol) (supplied by Kuraray). However, in that case The heat resistance value (former WATT 91 value) was mea-
aluminium chloride (Sigma-Aldrich) was used as the external sured according to EN 14257. For practical applications, a mini-
cross-linking agent, and NMA (Cytec) as the internal cross- mum value of 7 N/mm2 after 1 h exposure at 80 °C is usually
linking agent. Moreover, 1,6–dihydroxy–2,5–dioxyhexane (Lan- considered an acceptable value for a D3 glue intended to be used
xess) was used as biocide; for wood; the creep resistance value was measured according to
– formulation C was prepared by a different, not-conventional, [22], which considers that specimens must withstand a predefined
polymerisation system, always in the presence of highly constant load during a period of at least 21 days.
hydrolysed, medium molecular weight, poly(vinyl alcohol) (also Finally, wood failure percentage was visually determined in
supplied by Kuraray). However, in the polymerisation of adhe- accordance
sive C the initiation was switched from red-ox to thermal type, with [23].
and Vitamin C (Sigma-Aldrich) was introduced as the reduction
agent as an alternative to sodium formaldehyde sulfoxylate. 3.2. Corrosion tests
Moreover, an alternative protective colloid to be used in the
polymer emulsion was considered, with the aim of reducing the Investigation on potential corrosion problems has been carried
hydrophilic properties of the polymer. All this allowed synthe- out by soaking 5 cm diameter dishes made of AISI 420 steel in
sising the product without the specific addition of neither an 500 g of adhesive for a time period of 15 days at 50 °C. Then, the
internal nor an external cross-linking agent. Further details can dishes were cleaned and the surfaces observed.
be found in [19].
3.3. Formaldehyde emissions
Measurements on assemblies were carried out on four different
wood species commonly used in the woodworking industry, and Formaldehyde was measured both as content in the dispersion
on the polymeric films applied to wood surfaces. The used wood and as emission from glued joints. Measurements in dispersions
species were: oak (Quercus sp.p.), beech (Fagus sylvatica L.), cherry were carried out according to internal Vinavil method MVANS017,
(Prunus sp.p.), and maple (Acer sp.p.). Wood samples for all tests based on the reaction between formaldehyde and acetylacetone to
were taken from boards stored in standard conditions (20 °C and form a yellow-coloured complex and the subsequent quantitative
65% relative humidity), corresponding to approximately 12% of determination by UV/visible spectrometry at 420 nm wavelength.
moisture content in the wood. The determination was performed on the serum obtained by
centrifugation at 14,000 rpm of the dispersion diluted with water.
The formaldehyde emissions were measured in glued joints
3.1. Mechanical and physical characterisation
prepared with three products: in addition to adhesives A and C,
one commercial, low-formaldehyde content, UF glue (class E1) was
Physical-chemical characteristics of the two formulations (solid
also used. The latter product has been commonly used in appli-
content, Brookfield viscosity, pH and Minimum Film Forming
cations similar to those of D3 PVAc glues. Measurements were
Temperature, MFFT) were measured according to the standards
carried out according to [24] (gas analysis method). Joints were
used for water-based PVAc dispersions (they are detailed in
prepared assembling one beech thin board (400  50  5 mm3)
Table 1). Shear strength was evaluated in joints prepared by gluing
with a beech veneer (0.6 mm thickness). The choice of solid beech
beech (F. sylvatica L.) specimens in both normal climate and after as both the substrate and the veneer was suggested due to its
accelerated ageing, according to [4]. Tests in normal climate were known low emission of organic compounds [25–27], with the
intention of limiting the contribution of wood in the formaldehyde
Table 1
emission of the bonded assembly.
Main physical properties of PVAc adhesives A and C.
Moreover, panel edges were not covered with edge-bands, with
ANALYSIS Adhesive A Adhesive C the aim of magnifying the measured emission values. Finally, the
emissions of a similar assembly only prepared with Adhesive C
Solid content (110 °C  15 min.), % 527 1 48 7 1 were also measured according to the so-called Chamber method
Brookfield viscosity (RVT 20 rpm), mPa s 15,0007 3000 11,5007 2500
pH 3.0 7 0.2 4.5 70.5
[28].
MFFT, °C þ3 þ3 In all prepared assemblies, the adhesive content was 150 g/m2,
Bonding strength after 5 min, N/mm2 4.0 4.0 applied pressure 0.8 N/mm2, pressure time 2 min, temperature
Bonding strength after 15 min, N/mm2 6.5 7.0 90 °C for the UF system, 23 °C and 70 °C for all PVAc dispersions.
Bonding strength after 30 min, N/mm2 8.0 8.5
Bonding strength in normal climate, N/mm2 16 18
(condition D1 of EN 205) 3.4. Chromatic alteration after exposure
Bonding strength at the wet state, N/mm2 3.0 2.5
(condition D3-3 of EN 205) The two adhesive films (supported on a PE plate) were condi-
Wood failure, % 100 70 tioned at 80 °C (with uncontrolled relative humidity) for 1 h in an
Creep test (EN 14256), days 421 421
Heat resistance 80 °C (EN 14257), N/mm2 7.8 7.2
oven. In a different series, both adhesives were first spread on
specifically prepared plates of the selected wood species, and then
106 F. Chiozza, B. Pizzo / International Journal of Adhesion & Adhesives 70 (2016) 102–109

subjected to a continuous exposure to UV radiation at constant
temperature and humidity. The evaluations were obtained after 1,
5, 15, 30 and 60 min. The conditions set in the weatherometer
were: wavelength 340 nm, emitting power 0.35 W/m2, air tem-
perature 50 °C, relative humidity 65%, total duration of the expo-
sure 128 h. In each sample exposed to the weatherometer, an
aluminium foil was used in order to protect the upper half of the
surfaces from the direct irradiation, with the aim of differentiating
the effects only related to the environmental parameters from
those related to radiation.
and creep resistance) (Table 1). Therefore, the different poly-
merisation system adopted for Adhesive C did not induce sub-
stantial modifications in either the macroscopic properties of the
commercial product or the final characteristics of the wood joints.
This represents a very good result, because the vinyl acetate
polymerisation process is a complex and delicate route, which is
regulated by both thermodynamic and kinetic aspects and where
altering some ingredients or reaction procedures could also bring
unpredictable results, due to the interplay of the various factors
and variables involved in the manufacturing of latexes [18].

3.5. Colorimetric measurements

Table 2
Formaldehyde content on the considered PVAc D3 glues.
Colorimetric measurements were carried out by means of a
Spectrophotometer Minolta CM-2002 by using the chromatic HCHO content, ppm (method MVANS017)
system CIE L*a*b*; colour variations were calculated by comparing
Adhesive A 150
the values for each adhesive layer applied to wood between the Adhesive C o 10
UV exposed surface and the one covered by the aluminium foil.
Moreover, the influence due to wood discoloration was measured
by applying the same procedure to the wood substrate itself.
Table 3
Measurements were collected in different areas of both the
Formaldehyde emissions of the considered products at various temperatures.
adhesive layers and the wood surface, just after the end of the
ageing cycles, and the average values were calculated accordingly. Product T Pressing time Formaldehyde emissions (EN 717-2)
°C min mgHCHO/m2h

UF 90 2 0.4
4. Results and discussion Adhesive A 70 2 o 0.1
Adhesive C 70 2 o 0.1
The characterisation of formulations A and C indicated how the Adhesive A 23 120 0.3
two dispersions were equivalent in terms of general character- Adhesive C 23 120 o 0.1
istics, also including rheology and mechanical properties when
applied to wood substrates (namely shear strength, heat resistance

Fig. 5. Corrosion effect on adhesive A (a) and adhesive C (b). In (a) the effects of steel corrosion, on the right side of the disc, have been evidenced with a circle.
 F. Chiozza, B. Pizzo / International Journal of Adhesion & Adhesives 70 (2016) 102–109 107

Fig. 6. Differences in glue colouring between adhesive A and C after exposure at 80 °C for different periods of time.

Fig. 7. Differences in discoloration between adhesive A and C after UV exposure when applied to different wood species.

The only relevant difference between the prepared adhesives Table 4

was the acidity, the pH value of adhesive C being appreciably Colorimetric measurements obtained for the two adhesives (A and C) applied to
wood and for the wood itself after 95 h UV irradiation. In the table, ΔE* is the total
higher than product A (4.5 and 3.0, respectively, Table 1). This
colour difference, ΔC* is the chroma difference, and ΔL* the lightness difference.
difference was related to the different polymerisation processes: in
the case of C the use of NMA as cross-linker was excluded, and this ΔE* ΔC* ΔL* ΔE* ΔC* ΔL*
also allowed avoiding the use of any Lewis acid (including alu- Product Beech Maple

minium chloride), because it was not necessary to lower the dis-

Wood as such 10.2  9.3  3.9 15.5  13.8  7.0
persion pH to foster the cross-linking reaction. A 17.0  14.1  9.6 22.5  19.2  11.7
In turn, performing polymerisation without chlorides also C 9.2  8.4  3.4 16.0  14.0  7.8
allowed preventing (or, at least, appreciably limiting) the corrosion
problem in steel. This was proved by the corrosion tests: Fig. 5a Product Oak Cherry
shows a photograph of the steel plate after 15 days at 50 °C with
Wood as such 10.3  8.5  5.8 10.2  6.9  7.5
adhesive A, whereas Fig. 5b shows the same effect with adhesive
A 9.2  4.2  7.9 15.0  1.7  12.9
C, indicating how this latter product did not attack the surface C 7.5  4.6  5.9 5.5  3.5  4.3
of steel.
The specific values of free formaldehyde content for the two
considered dispersions are reported in Table 2. Measurements to both the absence of the conventional cross-linking agent and
confirmed the fact commonly known that the formaldehyde con- the new initiator used in the newly developed product, and indi-
tent of conventional D3 PVAc water based dispersions is lower cates once again the importance of these products in determining
than 200 ppm. As expected, the formaldehyde content in adhesive the formaldehyde content of the dispersions.
C was very low: it was below the minimum detectable value of the The formaldehyde emissions of the considered products used
used method (10 ppm), and therefore it can be assumed that as glues to veneer the wood panels are reported in Table 3. Wood
adhesive C does not generate formaldehyde. This fact is imputable assemblies were set in equivalent conditions among them, except
108 F. Chiozza, B. Pizzo / International Journal of Adhesion & Adhesives 70 (2016) 102–109
for drying temperature. As suggested by the supplier, 90 °C was
selected for the UF system in order to release the highest amount
of formaldehyde during the assembling operations, thus mini-
mising its emission in the final manufacture. Despite the different
drying temperatures, emission with the UF was higher than the
ones in PVAc glues. Instead, while measurements carried out at
70 °C did not indicate any practical difference between the two
PVAc products, the results from panels assembled at 23 °C allowed
evaluating the different emissions between adhesive A and C, thus
pointing out the importance of the setting process in the for-
maldehyde run out from assemblies. On the other hand, the dif-
ferent emissions observed at low temperature reflected the mea-
sured difference in the formaldehyde content of the dispersions
(Table 2). The method we used to evaluate assemblies emissions,
the so-called Gas analysis method [24,31], is considered (together
with the Perforator and the Flask ones) a derived procedure of the
Chamber method [28], which is usually thought as the reference
procedure for formaldehyde emissions. According to the most
recent regulations, in the majority of European countries, wood
panels (coated, overlaid or veneered) should comply with E1 class
requirement, which means that the formaldehyde release should
be below 0.124 mg/m3 (equivalent to 0.1 ppm when measured
according to the Chamber method) [29]. Nevertheless, the current
trend in terms of formaldehyde release for wood panels is to
introduce an extra class requiring a stricter value of emissions. In
this case, the field of application of that class comprises unfaced,
coated, overlaid or veneered wood-based panels. At the moment,
it seems that the requirement of maximum release in for-
maldehyde should be 0.080 mg/m3 (equivalent to 0.065 ppm).
However, some voluntary regulations diffused in Europe (such as
the RAL-UZ38, the environmental label so-called “Blue Angel”)
provide a formaldehyde emission limit threshold of 0.05 ppm [30],
whereas the Japanese emission class F4* indicates a limit equiva-
lent to ca. 0.04 ppm in the European chamber test [29].
Specific measurements carried out with adhesive C according
to the Chamber method [28] indicated how the emissions of this
product were only 0.010 ppm: this means that the only product
(among those considered) potentially complying with the strictest
requirements in terms of formaldehyde emissions is adhesive C.
Moreover, as expected adhesive C did not exhibit any chromatic
alteration after exposure at 80 °C (Fig. 6). In contrast, the effect of
discoloration after UV irradiation strongly depended on the wood
species to which products were applied, and it was most pro-
nounced in cherry and maple (Fig. 7). The same occurrence was
also found with colorimetric measurements: ΔL* variations were
always negative in all the three considered surfaces (i.e., wood
only, product A applied to wood, and product C applied to wood),
thus indicating a decreased lightness after exposure (Table 4). The
highest values of the ΔL* decrease were associated with both
cherry wood and maple (  12.9 and  11.7, respectively, both
related to product A), whereas the lowest value was observed in
beech (  3.4 in the case of product C).
It clearly appeared that the behaviour of product C compared to
A was different: the variation in ΔL* associated with wood only
and for C was always lower than 1 (except for cherry wood, but in
that case ΔL* for wood was higher, and not lower, than in C, i.e.,
the surface was lighter). Instead, for product A values of ΔL* were
almost double compared to wood (Table 4). Similarly, measure-
ments of chroma in A showed that the highest variations were
associated with maple and beech (  14.1 and  19.2, respectively),
thus indicating a more opaque appearance of surfaces, whereas
ΔC* was similar between the two products in the case of both oak
and cherry wood (Table 4). This appreciable different behaviour
between the two adhesives when applied to wood was imputable
to the absence in C of any aluminium compounds, which pre-
vented the formation of aluminium-flavonoids complexes. These
complexes were previously shown to be the reason for the marked
adhesive chromatic alteration after an energy impulse (such as
high temperature or UV irradiation) is applied to PVAc products
spread on selected wood species [10].
5. Conclusion
This work has described the chemistry of conventional PVAc-
D3 products, highlighting the reasons for the main inconveniences
encountered with these adhesives at an industrial level. It was
shown how avoiding the conventional cross-linker, changing the
protective colloid in the polymer emulsion, using a thermal
initiator instead of a red-ox one, introducing Vitamin C as the
reduction agent, and eliminating the formaldehyde-releasing
ingredients from biocides has allowed the development of new
products in which the previously discussed problems are elimi-
nated or, at least, minimised. Moreover, the adopted polymerisa-
tion system did not substantially change both the macroscopic
properties (except for the pH value) and the final characteristics of
wood joints compared to conventional D3 dispersions. All these
occurrences were verified by specific tests: the new product did
not corrode steel (because of both the higher pH value and the
absence of any chlorides), it did not contain formaldehyde, and
therefore did not emit this carcinogenic volatile compound (thus
potentially complying with the strictest of requirements in terms
of formaldehyde emissions in the wood industry sector), and
moreover it did not exhibit any aesthetic defects as a consequence
of the glueline chromatic alteration after exposure to both tem-
perature and UV irradiation, or wood staining (thanks to the
absence of any aluminium compounds and to the low acidic
conditions).
The present work also showed how understanding the specific
role of the chemical compounds generating unpleasant incon-
veniences, studying alternative raw materials, and applying a new
chemical approach, represents an efficient way to produce inno-
vative PVAc water-based dispersions belonging to class D3.
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