ISSN 1995-4212, Polymer Science, Series D. Glues and Sealing Materials, 2009, Vol. 2, No. 1, pp. 8–15.

© Pleiades Publishing, Ltd., 2009.

Original Russian Text © A.E. Chalykh, V.Yu. Stepanenko, A.A. Shcherbina, E.G. Balashova, 2008, published in Klei. Germetiki. Tekhnologii, 2008, No. 7, pp. 2–8.

Adhesive Properties of Ethylene and Vinyl Acetate Copolymers

A. E. Chalykh, V. Yu. Stepanenko, A. A. Shcherbina, and E. G. Balashova
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninskii pr. 4, Moscow, 119991 Russia
e-mail: chalykh@mail.ru, tsiv@phyche.ac.ru
Received March 20, 2008

Abstract—Surface properties of ethylene and vinyl acetate copolymers (EVAs) are considered depending on
their composition and history of surface formation. The kinetics of structural transformations in the near-sur-
face layers of copolymers is investigated. Relaxation times and the equilibrium state of the EVA surface are
determined. The orrelation dependence between the surface energy of copolymers and their adhesive properties
for substrates of different natures is constructed.
DOI: 10.1134/S199542120901002X

SURFACE ENERGY, HISTORY
OF THE EFFECT OF SURFACE FORMATION
EVA copolymers are widespread adhesives that are
often used in polymer material science as hot melts for
substrates of different natures (metals, wood, paper,
leather, polymers) [1, 2]; their adhesive properties have
been investigated many times and are described in a
variety of original articles and reviews [1–7]. Thus, in
[8, 9], the strength of EVA adhesive compounds (ACs)
was investigated depending not only on the copolymer
composition and nature of the substrate, but also the
interdiffusion in the adhesive–substrate system. Over
the last few years, investigations have been conducted
concerning the adhesive properties of blends of EVA
with different compositions [5]. However, many ques-
tions concerning how adhesive compounds of this class
of glues with different substrates are formed, as well as
the effect of thermokinetic conditions of the formation
and decomposition of compounds, remain open. There
are several reasons for this. At present [10–13], the
strength of adhesive compounds (A) measured under
different experimental conditions has been found to
depend on three parameters, i.e., σ0, S, and ψ, which are
connected with each other by the simple equation
A ≈ k ( σ 0 S + ψ ),
where σ0 is a known specific adhesion caused by attrac-
tive forces on the interfacial boundary or in the transi-
tion region in the case of “ideal molecular contact of
conjugated phases” [14]; S is an apparent area of con-
tact, which determines the adhesive coherence of the
substrate–adhesive system; and ψ is a parameter that
characterizes the material’s response to external
mechanical action [8].
It is obvious that, according to this conception, the
investigation of the adhesive properties of copolymers
means not only measuring the strength characteristics
of adhesive compounds, but also obtaining information
about every parameter in equation (1) depending on the
composition of the copolymer and the nature of the sub-
strate surface. This in turn requires the use of additional
independent studies. For instance, it was shown in work
[14], that the ideal adhesive strength σ0 is connected
with thermodynamic work of adhesion WA by the equa-
tion
σ 0 ≈ k ( W A / X 0 ), (2)
where X0 is the equilibrium distance between two
phases and k is a constant. Recall that the thermody-
namic work of adhesion WA = γA(1 + cos θ). For the well
wetting of the surface of substrate adhesives, which is
one of the most important conditions for the formation
of high-quality adhesive compounds [15], cos θ must be
close to unity, so that 1 + cos θ ≅ 2. Therefore, WA ≅ 2γA,
where γA is the surface tension or surface energy of
adhesive. By substituting the received equation into (2),
we obtain
σ 0 ≈ 2k ( γ A / X 0 ). (3)
(1) Thus, in order to characterize parameter A, an inde-
pendent measurement of the composition of the copol-
ymer and the effect of its thermal history on the ener-
getic characteristics of an EVA surface should be
carried out and the relaxation and rheological charac-
teristics of copolymers under conditions of formation,
as well as decomposition, should be investigated.
The goal of the present work is to investigate the
energetic characteristics of ethylene and vinyl acetate
copolymers depending on their composition, phase
nature, and thermal history and to construct the correla-
tion dependences between the thermodynamic work of
adhesion and peel strength of adhesive compounds (A).

8
 ADHESIVE PROPERTIES OF ETHYLENE AND VINYL ACETATE COPOLYMERS 9

Table 1. Characteristics of copolymers under investigation

Degree
EVA brand Designation VA content, wt % Density, g/cm3 Tm.p., °C
of crystallinity, %
11104-030 EVA-7 7 0.925 25.5 103
11306-075 EVA-14 14 0.928 16.6 97
12306-020 EVA-20 20 0.940 7–9 70
11808-240 EVA-29 29 0.956 3–4 60
11708-1250 EVA-30 30 0.956 3–4 60
12508-150 EVA-40 40 0.960 ~3 25

EXPERIMENTAL tion did not exceed 1 grad, which corresponds to the

The following EVA copolymers containing different error of surface energy definition equal to ±0.1 mJ/m2.
amount of monomeric units of vinyl acetate were used: P D
EVA-7, EVA-14, EVA-20, EVA-29, and EVA-30 poly- Polar γ S and dispersive γ S components of surface
mers produced by OAO Sevilen; some of their charac- energy of EVA were calculated by the Owens–Wendt
teristics are presented in Table 1. equation [18]
Figure 1 presents a phase and physical state diagram
P D
2 γ S γ lv 2 γ S γ lv
D D
of EVA copolymers [16]. It can be seen that three states
are characteristic for these copolymers, i.e., melt and 1 + cos θ = ------------------------
- + ------------------------- . (4)
γ lv γ lv
semicrystalline, the amorphic phase of which exists in
the high-elastic and glassy states. The degree of cristal- For greater convenience, equation (4) as reduced to
linity (Table 1) decreases with an increase in statisti- the following form:
cally distributed units of vinyl acetate in a chain and, if
the vinyl acetate content is greater than 30%, the crys- P
talline state of copolymers degenerates. γ lv ( 1 + cos θ ) D P γ lv
--------------------------------- = γ S + γ S ------
D
-. (5)
All experiments were carried out on EVA films with
2 γ lv
D
γ lv
widths of 150–200 µm, which were obtained by hot
molding in contact with high- (aluminum) and low-
energy (PTFE) substrates at T = (Tm.p. + 10°) and a pres-
sure of 2 MPa. The samples were kept at this tempera- T, °C
140
ture for 25–30 minutes, after which they were slowly 1
cooled (~3 deg/min) to room temperature. Then, EVA 2
120
films were adhesively peeled from the substrates. For Tann 3
the formation of samples in contact with air, EVA gran- 100
ules were melted in a thermal oven at T = (Tm.p. + 50°)
with subsequent slow cooling. 80
A portion of the thus prepared samples were Melt
exposed to thermal annealing at temperatures higher 60
(Tm.p. +5°) and lower (Tm.p. –5°; Tm.p. –20°) than the
melting points of copolymers (Fig. 1). The time of 40
annealing varied from several minutes to several hours; Texp Crystal
as in a stage of film preparation, after annealing, they 20
were cooled to room temperature with a set permanent
rate. 0
The surface energies of copolymers were deter-
–20
mined by the method of the sedentary drop of test liq- Glass
uids (Table 2). Drops were sized 1–2 mm3. Measure-
ments of interfacial angles (θ) were carried out at (25 ± PE 20 40 60 80 PVA
0.5)°C on an optical horizontal microscope with gonio- wVA, wt %
metrical scale. The measurement procedure did not dif-
fer from that traditionally used [17]. Left and right Fig. 1. Phase diagram of EVA copolymers. (1) origi-
angles of 10–12 drops of every test liquid were mea- nal experimental data; (2) literature data [3]; (3) con-
sured. The statistical processing of the measurement ditions of thermal annealing of samples (Tann). Texp,
results showed that errors in the interfacial angle defini- experiment temperatures.

POLYMER SCIENCE Series D Vol. 2 No. 1 2009