therm0chimica

acta
ELSEVIER Thermochimica Acta 287 (1996) 53 70

Phase miscibility in oil/resin mixtures"

a study by FTIR and thermomechanical analysis
O . P a g 6 s a,b,,, B. L e g e n d r e b, M . O d l y h a a, D . C r a i g c
a Department of Chemistry, Birkbeck Colleye, 29 Gordon Square, London WCIH OPP, UK
b Laboratoire de Chimie-Physique Minkrale et Bioinoryanique, Facultb de Pharmacie, 5 rue J.B. Cldment.
92296, Ch~tenay-Malabry, France
c Department ~]'Pharmaceutics, The School of Pharmacy, 29/39 Brunswick Square, London WCIH lAX. UK
Received 28 December 1995; accepted 29 March 1996

Abstract

Quantitative infrared analysis in the carbonyl region with a simple curve-fitting procedure and
thermomechanical measurements were used to analyse critical behaviours in naturally aged
oil/resin mixtures covering a wide range of composition. The results are discussed on the basis of
a comparative study performed with fresh mixtures of the same composition, used as standards,
and a phase miscibility analysis.
Thermomechanical measurements give macroscopic evidence for phase segregation in nat-
urally aged mixtures with a resin component content strictly below 50%, while above this
threshold the basic components are totally involved in the formation of a stable mixed oil/resin
phase. At the molecular scale, infrared measurements appear to be sensitive to the subsequent
oil/resin interaction in aged mixtures which appears to develop at the first stage of the mixing.

Keywords: Ageing; Oil/resin systems; Phase segregation; Quantitative infrared; Thermomecha-

nical analysis

1. Introduction

Because they exhibit a s t r o n g t h i x o t r o p i c c h a r a c t e r at r o o m t e m p e r a t u r e at the

initial stage of mixing, oil/resin systems c o n s t i t u t e a t t r a c t i v e m e d i a for n a t u r a l paints.

Corresponding author; Now at laboratoire de chimie-physique min6rale et bioinorganique, facult6 de

pharmacie, 5 rue J.B. Cl6ment, 92296 ch~.tenay-Malabry France. Fax : (33) 146 83 54 54; e-mail : olivier, pages
/a!cep. U-psud.fr

0040-6031/96/$15.00 (~?)1996 - Elsevier Science B.V. All rights reserved

P l l : S0040-6031 (96)02992-9
54 O. Pages et al./Thermochimica Acta 287 (1996) 53 70

Nevertheless, their use is rather constrained as large variations in the physical

properties of aged mixtures are generally observed as a function of their composition.
This work provides evidence of critical behaviour in definite concentration ranges of
the basic components in naturally aged mixtures. These are observed by thermo-
mechanical (TMA) and infrared analysis (FTIR) and discussed on the basis of a com-
parative study with fresh mixtures of the same composition, used as references. While
the TMA technique provides information at the macroscopic level on the mechanical
properties of the mixtures, FTIR measurements support the study at the mesoscopic
level and allow recognition of physical interactions, if any, between their basic
components [1-3]. The interpretation of the FTIR data is supported by a simple
curve-fitting procedure performed in the carbonyl region of the absorption spectra.
Finally, a natural correlation is expected between the behaviour of the mixtures
deduced from the combined TMA/FTIR analysis and the quality of their phase
miscibility as observed by eye.

2. Materials and techniques

2.1. Materials

Linseed oil consists of a mixture of triglycerides with a range of saturated and

unsaturated long-chain fatty acids [4] up to C18 One volume of lead-oxide-based drier
was added drop by drop at room temperature to 8 volumes of linseed oil in order to
form the oil component. Mastic is a triterpenoid natural resin [4] (C3o); 10 g of mastic
resin were dissolved at 80C in 50 ml ofoil of turpentine monoterpenoid (Clo) in order
to form the resin component. A magnetic stirrer was used as the mixer. Both mixtures
were stirred at low and constant speed during the adding process and again 30 min after
so as to obtain clear, homogeneous substances.
Five oil/resin systems were prepared with the oil and resin components described
above as starting materials. They correspond to volume proportions of the resin
components of 25%, 33.3%, 50%, 66.6% and 75%, and are respectively labelled as
mixtures 1-5. The procedure consisted of placing the appropriate volume of the oil
component in the mixer and adding the resin component drop by drop with the stirrer
set at low speed. Once the full amount of the resin component had been added, the
mixture was stirred for 10 min at low speed to ensure homogeneity, and then transfer-
red to a quart bottle and capped to prevent evaporation. A piece of ordinary aluminium
foil was used as a liner for the screw caps of the quart bottle. All mixtures have a gel
consistency at room temperature. After their preparation, all the mixtures appear as
homogeneous gels.
Some of the measurements were performed with naturally aged materials. After their
preparation, these were deposited as thin films on glass substrates and left in the open
air at room temperature and in the dark for 5 months.
Labels 1-5 are relative to the composition of the mixtures and design, independent of
fresh and naturally aged materials. Volumes and weight were respectively accurate to
0.2 ml and 0.01 mg.
 O. Pages et al./Thermochimica Acta 287 (1996) 53 70 55

2.2. Techniques

Differential scanning calorimetry (DSC) measurements were performed with a con-

stant heating rate using a Seiko 220C instrument: the heat flow between the sample and
the reference, placed in open crucibles within a Boersma-like calorimeter, is recorded as
a function of the temperature with the endothermic (positive) position downward. N-,
was used as a purge gas. The principles of the analysis of the DSC measurements are
described more extensively elsewhere [5, 6].
FTIR spectra were acquired from 4000 to 650cm 1 at 4 cm-m resolution using
a TGS detector, and averaged over 30 scans. They were run unpurged and the data
collection time was 2 min. Two different methods were used to perform infrared
measurements according to the nature of the mixtures. The details of the principles [-7]
and techniques [8] are described more extensively elsewhere.
As fresh materials present contact properties similar to those of a liquid, their
infrared spectra were collected with the attenuated total reflectance (ATR) technique.
The absorption volume is fixed by the refractive index which has the same value for the
oil and resin components, namely 1.5. In these conditions the same absorption volume
is investigated in all the mixtures which allows the direct comparison of their infrared
signal. ATR spectra were analysed by a Micolet 510 spectrometer; the crystal fitted to
the ATR equipment was a 12-reflection ZnSe 45 ~.
Because of high surface roughness which prevents good quality contact at the
ZnSe-sample interface, satisfactory ATR spectra from naturally aged mixtures could
not be obtained. An arbitrary amount of each sample was removed from the
glass substrate, placed on a KBr disc, and heated at 60~C so as to soften the material
and remove the voids in the bulk. The latter resulted from the evaporation of the
oil of turpentine and led to a parasite diffusion of the infrared light which greatly
affected the quality of the spectra. The heating process lasted 30 s, after which a
second KBr disc was placed over the sample and pressed on the first. The whole
structure was then removed from the oven and analysed by transmission. As the
thickness of the sample is not monitored, a direct comparison of the infrared spectra
was not possible. Infrared spectra recorded in transmission with the oil and resin
components using the same definite pathlength were used as references for the analysis
of the above mixtures.
Thermomechanical measurements were performed in penetration mode, under the
controlled force procedure, with a Perkin-Elmer 7 series thermal analysis system, using
a cylindrical probe, 1 cm in length and 1 mm in diameter. TMA curves were recorded
from - 6 0 : C up to 100c'C at a heating rate of 2 C m i n 1 Static forces of 1 mN and
10 mN were respectively applied to the fresh and naturally aged mixtures. For some
specific samples, different static forces were applied in order to reveal clearly their
softening transitions.
Fresh and naturally aged mixtures, and their basic components, were analysed in
circular crucibles, 3 mm in diameter and 1 mm in height, so as to define a fixed geometry
for all the measurements. Fresh mixtures and the basic components were poured
directly in the crucibles. In order to investigate the bulk rather than the surface
properties of naturally aged mixtures, large pieces of the thin films were removed from
56 o. Pages et al./Thermochimica Acta 287 (1996) 53-70

the glass substrates, deposited in the crucibles, and heated at 60C for 30 s, so as to
define a thick, homogeneous sample.
As the thickness of the samples was not monitored, a direct comparison of the TMA
curves was not possible; attention is then mainly focused on the positions of the
transitions.

3. Experimental results

3.1. D S C measurements

DSC analysis was used to determine the main thermodynamic transitions of the
basic components. DSC curves obtained with a constant heating rate of 7C min - 1 in
the temperature range from - 1 5 0 C up to 200C with freshly prepared mastic resin
and oil component are reported in Fig. 1.

3.2. F T I R measurements

ATR spectra of the lead-based drier, the oil, the oil of turpentine and the resin
component are reported in Fig. 2.
For each mixture and basic component, the shape of the infrared absorption
structures in the carbonyl region has been systematically analysed in a quantitative
way by a curve-fitting procedure using the same set of four Lorentzian functions. Their
characteristic parameters are reported in Table 1. The positions and widths at half
height were fixed; only the intensities were adjustable. ATR spectra obtained with the
basic components and the fresh mixtures are respectively reported in Figs. 3 and 4 with
the results of the curve-fitting procedure. For fresh materials, the evolution of the
carbonyl areas associated with the oil and resin components as a function of the
composition of the mixtures is reported in Fig. 5. Transmission spectra obtained with
the basic components and the naturally aged mixtures are respectively reported in
Figs. 6 and 7 with the results of the curve-fitting procedure. For fresh and naturally
aged materials, the evolution of the ratio of the carbonyl areas related to the oil and
resin components are respectively reported in Fig. 8a and 8b.

3.3. Thermomechanical measurements

The thermomechanical curves obtained with the oil component and the flesh
mixtures are reported in Fig. 9. Considering mixture 4, additional measurements were
performed under the same experimental conditions but with greater applied forces,
namely 10 and 50 mN. These are reported in Fig. 10. The thermomechanical curves
obtained with the naturally aged mixtures are reported in Fig. 11. From calibration
with pure distilled water, it appears that a typical experimental error of + 2C is to be
expected for the precision in the determination of the softening transitions.
 2500l
~(
8 0 0
O. Pages et al./Thermochimica Acta 287 (1996) 53 70

" "- : -- " J- ~ ' :"" " ;':"=-" : :':~':" -

-1,6
~
E~
57

--900 ~ e~
-9 ~0

t~ - 2600

-16,5

- 4300
L

'1

-6000 I I -24
-150 - 50 50 150 250

temperature / C

-50 -5

(b)
..=
-450
- 1,25
1"
Q~
~ -650 -~

-as .~

-1250 - C/~

-155o .~
$.

,'1

- 2050 II I I I - lO
-1~o -so 5o 1so 26o

temperature / C

Fig. 1. DSC curves obtained with a constant heating rate of 7C min 1 in the temperature r a n g e - 150"C to
250C with the oil component freshly prepared (a) and pure mastic resin (b). In each case, the measurements
were performed under the same experimental conditions with two different samples from the same material.
Labels 1 and 2 refer respectively to the DSC curve and its first derivative.

4. Discussion

T h e D S C m e a s u r e m e n t s a r e p r e s e n t e d first; t h e y w e r e u s e d as a b a s i s f r o m w h i c h t o
define the thermal context of the combined FTIR/TMA analysis.
 58 O. Pages et al./Thermochimica Acta 287 (1996) 53-70

L_
!
!
!

1=

t--
==

I I I
3000 2000 1000

i
2

L
I
q,l
!
1=
.a
t-- !
==
.t=

/
I I I
3000 2000 1000

W a v e n u m b e r / c m -t

Fig. 2. ATR infrared spectra obtained with the basic constituents of the resin (1) and the oil (2) components:
the resin component (1a); the oil of turpentine (1b); the oil (2a) and the drier (2b). The carbonyl region, where
the curve-fitting procedure is applied, is delimited by dashed lines.

4.1. D S C measurements

D S C c u r v e s o b t a i n e d w i t h the oil a n d resin c o m p o n e n t s s h o w t w o e x o t h e r m i c

t r a n s i t i o n s , at - 8 7 C a n d - 7 5 C , a n d t w o e n d o t h e r m i c t r a n s i t i o n s , at - 3 3 C a n d
 O. PagOs et al./Thermochimica Acta 287 (1996) 53-70 59

Table 1
Characteristic fixedparametersof the four Lorentzianfunctions used for the curve-finingprocedure

Lorentzian p e a k s Position/cm
-~ Halfwidth at fullheight/cm-1
1 1769 20
2 1742 15
3 1720 20
4 1703 15

rc, x3
b rc,

i 1
E~

1~oo 1"~oo lt~OO 1~oo 1700

' 1 6' 0 0

Wavenumber / cm ~ Wavenumber / c m -t

Fig. 3. ATR infrared spectra obtained with the resin (a) and the oil (b) components. Labels 'rc' refer to the
experimental curves. The Lorentzian structures used for the curve-fitting procedure are reported together
with the resulting fitting curve, labelled 'cf' for each material Numbers 1 to 4 refer to the corresponding
Lorentzian functionsin Table 1.

- 2 5 C . The first two processes are interpreted as partial crystallization processes

generated respectively by segmental and chain motions. When increasing the tempera-
ture, it is proposed that thermally activated molecular motions take place on the same
scale and destroy the macroscopic order. DSC structures located at - 33C and - 25~C
are thus interpreted as partial melting transitions.
As it is prepared with a high proportion ofoil of turpentine, which is highly volatile, it
is extremely difficult to perform successful DSC measurements with the resin compo-
nent. Consequently, basic information concerning thermodynamic transitions in the
resin component were extracted from DSC measurements performed with pure mastic
resin. DSC curves obtained with the latter material exhibit two exothermic transitions,
 t1.L
60 O. Pa#~s et al./Thermochimica Acta 287 (1996) 53-70

0.8 1
lJ _
31S~)O2600 1800 1860

3600 2.GO0 1800 1660 t600 10:00

0.8

U~
35'00 2600 1800 1~60 ,~'o. 1.;o

O.

3600 2600 '1800 16S0 100 10~

1
~;oo ~.0 '1.0 ,~'. 1500 1000

Wavenumber / c m -1

Fig. 4. ATR infrared spectra performed with fresh mixtures. Labels 1 to 5 refer to the corresponding
compositions of the mixtures. The Lorentzian structures used for the curve-fitting procedure are reported
together with the resulting fitting curve for each material.
 O. PagOs et al./Thermochimica Acta 287 (1996) 53 70 61

75t

601
55

50

L 45

40
0=

= 35
m

30
0
L. 25
,a
20

15-

10'

5'

0 i = = , i i = ' f i - = i

0 10 20 30 40 50 60 70 80 90 100

resin component content/%

Fig. 5. Infrared carbonyl areas deduced for the oil and resin components from the curve-fitting procedure
performed with fresh mixtures. Straight lines 1 and 2 represent the ideal expected areas in the mixtures when
considering a linear relation between the magnitude of the carbonyl areas associated respectively with the oil
and resin components alone (refer to Fig. 3) and their amount in the mixtures, solid and open circles refer to
experimental data.

at - 2 5 C and 140C, and two endothermic transitions, at 32C and 70C. In addition
thermomicroscopy observations performed with mastic resin from room temperature
up to 200C at a constant heating rate of 7C min 1 show that mastic resin changes
from a powder to a liquid when going through the transition at 70C, and undergoes an
irreversible alteration in colour from clear yellow to dark brown at 140C. Transitions
observed at 70 and 140C are thus respectively attributed to the melting [9] and the
denaturation of mastic resin. The two structures which appear at lower temperatures
are not assigned.
62 O. Pages et al./Thermochimica Acta 287 (1996) 53 70

rc !b
4-

rc
.0
L

L. .2-
0
0

1 C
!
1~00 1700 1~00 1800 1700
= q~00

Wavenumber / cm ] Wavenumber / c m -1

Fig. 6. Infrared spectra recorded in transmission with the resin (a) and the oil (b) components. They were
recorded with the same definite pathlength of 0.9015 ram, Labels 'rc' refer to the experimental curves. The
Lorentzian structures used for the curve-fitting procedure are reported together with the resulting fitting
curve, labelled 'cf for each material. Numbers 1 to 4 refer to the corresponding Lorentzian functions in
Table 1.

4.2. lnfrared measurements

4.2.1. Basic materials

Pure mastic resin appears as a dense powder at room temperature and parasite
diffusion due to voids in the structure greatly affects the quality of the ATR spectra. In
these conditions, basic information concerning the infrared responses of the constitu-
ent materials of the resin component were obtained from the comparison of the ATR
signals delivered by the resin component itself and the oil of turpentine. In the carbonyl
region, which spreads from 1550cm -1 to 1850cm -~, the oil of turpentine has
a negligible contribution to the infrared signal in comparison with the intense structure
located at 1702 cm - 1, attributed by difference to pure mastic resin. Concerning the oil
component, the lead-based drier has no contribution to the infrared signal in the
carbonyl region, while the structure at 1742 c m - 1 constitutes a clear indicator for the
oil. The carbonyl region thus appears to be the zone of choice to investigate the oil/resin
relation without considering, to a first approximation, the separate influences of the
lead-based drier and the oil turpentine. The latter will be discussed below.
To this end, a curve-fitting procedure has been developed in the carbonyl region.
A suitable set of Lorentzian function [10] has been chosen so that after the curve-fitting
the reconstructed oil-like contribution to the total absorption area of the resin
component does not exceed 5%, and vice versa. Using this procedure, with a small
 O. Pag;~s et al./Thermochimica Acta 287 (1996) 53-70 63

osi
L_
0.4

0
3;00~o ;., 16;o i
1600 10~)

o.f,
).4

3r~o 2800 i1800 1;60 1600 1000

k 0.8

=: 0.4

o
35~002600 1800 18~0 1500 1~00

0.4

35~0 2500 11800 16~0 lS100 10~0

0.4

~;oo ~oo 18oo 1.6o 1.o 1.'o.

Wavenumber / c m -~
Fig. 7. Infrared spectra recorded in transmission without a definite pathlength with naturally aged mixtures.
The Lorentzian structures used for the curve-fitting procedure are reported together with the resulting fitting
curve for each material. N u m b e r 1 to 5 refer to the corresponding mixtures.
64 O. Paoks et al./Thermochimica Acta 287 (1996) 53-70

tO.O &O

g.5-
b
7.5-
g.o-
7.0-

&O tlJ 0 e.s-

0
7.5,

7.0
s.s-
~J
6.5 L.
S.O-
6.0
% 4.S-
s.5
) O
5.O -~ 4.o-
ct
4.5

4,0
~ 3.0
3.5 q~
t- II,
U,
3.0-
mB
2.5- 0 2.0
0
2.0-
1.5
1.5.
1.0,
1.0-

0.5" 0,5

0.0
,5 ~; s; 4; s; e; ,~ - 15 25 35 45 55 55 ,5 ,5

resin component content / % resin component content / %

Fig. 8. Evolutionoftheratioofthecarbonylareasrelatedto theoiland resin components deduced from the

curve-fining procedure, as a function of the composition of fresh (a) and naturally aged (b) mixtures. Plain
lines correspond to the ideal curves expected when considering a linear relation between the magnitude of the
carbonyl areas associated with the basic components (refer to Fig. 3 and Fig. 6). Black dots correspond to
experimental data.

number of adjustable parameters, allows one (i) to fit satisfactorily the experimental
infrared spectra obtained with the oil and resin components; and (ii) to extract their
individual contributions to the total area of the absorption peaks obtained with the
mixtures. Considering point (i), two different sets of intensities were considered for the
Lorentzian functions, as measurements were performed differently with the ATR and
transmission techiques. Considering point (ii), the individual contributions of the oil
and resin components to the carbonyl signal of the considered mixture were recon-
structed from the calibration described above which resulted in a curve-fitting of the
carbonyl region with two ajdustable parameters. In each case, the difference between
the theoretical and the experimental carbonyl areas did not exceed 10%.

4.2.2. Fresh mixtures

The ATR technique allows a direct quantitative comparison of the carbonyl areas
from one mixture to the other because absorption volumes are identical for all the
 O. Pages et al./Thermochimica Acta 287 (1996 ) 5 3 70 65

;~ 120 120
]B
100 ,~ 100
Q

E
Ip 8O EQ 80
Q
60

\
~. 0o Q.

"0 40 40
O
O
,la 20 .a 20:
.o
n Q. 0
-80' t
-40 0i 40t 810 20
080' -40 ; 4tO 810 1'20
Temperature / C Temperature / C

120 120
1 4
100 1oo
Q q)
E
@ 8O E 8O
_m 6 o -~ 6O

"o 40 "o 40
o
,Q 20 ,~ a o
o o
a. 0 Q. I
-80 - 40 0 410 8~0 120 080 -40 0 40 80 120
Temperature / C Temperature / C

120 120
lOO 100
E 00 ~ 80
_a 6 o ~ 0o
m
1= 40 ~ 40
~ 2o ~ ao
.o .o
n. 0 ~- o-!
-81 - 40 ; 410 810 120 -;o ; ,'o 8'o ,20
Temperature / C Temperature / C

Fig. 9. T h e r m o m e c h a n i c a l curves o b t a i n e d with the oil c o m p o n e n t (a) and fresh m i x t u r e s with a static force
of 1 mN. Labels 1 to 5 refer to the c o r r e s p o n d i n g c o m p o s i t i o n s of the mixtures.

materials over the whole range of composition. In this case, distinct evolution of the
carbonyl areas associated with the oil and resin components can be considered as
functions of the composition of the mixtures. Quasi-linear evolutions are obtained;
determined ideally by the experimental points related to the oil and resin components.
The divergence between the experimental points and the ideal curves when approach-
ing small total carbonyl areas is attributed to the simple nature of the curve-fitting
procedure.
The infrared responses of the oil and resin components in fresh mixtures correspond
ideally to the individual responses of these materials multiplied by their content in the
mixtures.
66 O. Pages et al./Thermochimica Acta 287 (1996) 53- 70

| eo

~ 2,
'!
"f
40
a

L 0 J i
* . 20
Temperature / *C

100

~ 4O

~ ~o
o. 0 r
-80 -40 0 40 810 120
Temperature / "C

so!
120
~100
j.o
"
~ 4o
~ ,0
I '
o. O. 0 120
Temperature / C

Fig. 10. Thermomechanical curves obtained with m i x t u r e 4 w i t h d i f f e r e n t static forces of 1 mN(a), 1 0 m N ( b )

and 50 m N (c).

4.2.3. Naturally aged mixtures

Infrared spectra of naturally aged materials were recorded in transmission and the
absorption volumes were not monitored. In order to eliminate this unknown par-
ameter, the analysis was concerned with the evolution of the ratio between the carbonyl
areas of the oil and resin components as a function of the composition of the mixtures.
The similar evolution obtained with the fresh mixtures is also considered. Each of these
was compared with the ideal curve obtained from the sole consideration of the infrared
spectra of the basic components recorded with the same absorption volume but
different techniques (ATR or transmission when considering respectively the fresh and
aged materials).
 O. Pagbs et al./Thermochimica Acta 287 (1996) 53-70 67

120
3

| 100

! 60
i"
40 \
2O
110
rL i
~100 --~ 0 4 0 - 2 0 0 20 40 60 8t0100120
i
~ 8o
Temperature / *C

"~ 80
{ 5o
i 120
4
o. 4 0 4 0 - 2 0 0 20 40 80 80100120
Temperature / C 1oo
o
E 8o
a 6o
.o
o
2O
.o
"t2
100
F "~2
040"20 0
i
20 40 6'0 8'0100120

i
~. 6o
Temperature / C

~ 4o
~ ~o
i i 120
~" ,0-i0 ; 20 40 s'o 8'ot;olzo 5
Temperature / C too
Q
E 80
68
M
40

20
~- 0.,
Temperature / *C

Fig. 11. Thermomechanical curves obtained with naturally aged mixtures with a static force of 10 raN.
Lables 1 to 5 refer to the corresponding compositions of the mixtures.

While for fresh mixtures the experimental points agree with the ideal curve, a clear
discordance is observed for naturally aged materials. This discordance is characterized
by three points: (i) strictly below a resin component of 50%, the ideal curve constitutes
a large over-estimation of the experimental points; (ii) from a resin component content
of 50%, the trend is reversed; (iii) there is an exception singularity for the resin
component content of 66%.
68 O. PaoOs et al./Thermochimica Acta 287 (1996) 53-70

Two different phenomena accompany the ageing process of the oil/resin mixtures.
Firstly, the polymerization of the oil component, enhanced by the drier, leads to the
formation of a tri-dimensional network of triglyceride units [11]. Secondly, the
progressive loss of the volative constituent of the resin component, namely the oil of
turpentine, increases the density of the structure of the mixtures. The latter process does
not affect the carbonyl region of the infrared spectra as it merely corresponds to the
disappearance of the weak structure located at 1680 cm- 1. However, the polymeriz-
ation process induces a decrease in the intensity of the infrared signal in the carbonyl
region [10]. It is therefore taken as being responsible for effect (i). When considering
only the polymerization process, the above-mentioned over-estimation should be
observed over the whole composition range but with decreasing amplitude as the oil
component content decreases, which is in contradiction with points (ii) and (iii). The
corresponding behaviours are discussed in more detail below.

4.3. Thermomechanical measurements

4.3.1. Basic materials

The thermomechanical curve of the oil component shows only one softening
transition, at -25C. Its assignment is given by the DSC measurements. Because the
resin component does not freeze a b o v e - 150C, thermomechanical analysis could not
be performed with this material. From the DSC measurements, a major softening
transition due to the resin is expected in the neighbourhood of 70C.

4.3.2. Fresh mixtures

The thermomechanical curves are characterized by four points the first two being
rela'ted to the characteristic temperatures of the softening transtions, and the others to
the relative magnitude of the corresponding probe displacement with respect to the
baseline: (i) mixtures 1 and 2 show only one softening transition located 10C below
that of the oil component; (ii) two softening transitions, in the regions of - 35C and
75C, are observed with the other mixtures (iii) the amplitude of the probe displacement
associated with the low-temperature transition decreases non-linearly with the compo-
sition when going from mixture 2 to mixture 3; (iv) high applied forces of 10 and 50 mN
were necessary to reveal all the softening transitions of mixture 4.
The softening transitions mentioned in point (i) are attributed to the oil compo-
nent. It is suggested that the resin component acts as a plasticizer of the oil component
in oil- rich mixtures, and it is therefore taken as being responsible for the low-
temperature shift of 10C. The low- and high-temperature transitions observed with
mixtures 3, 4 and 5 are clear indicators of, respectively, the oil and resin components.
Points (iii) and (iv) indicate respectively an unexpected increase in the density for the
mixtures with a resin component content superior to 50%, and an exception for
mixture 4.
While the softening transitions of the basic components remain unaffected by
mixing, an effective oil/resin interaction has to be considered, whatever its nature, to
explain the non-linear mechanical properties in mixtures with a resin component
content above 50%, with an exception for the resin component content of 66%.
 O. Pagds et al./Thermochimica Acta 287 (1996) 53-70 69

4.3.3. Naturally aged mixtures

The thermomechanical curves are characterized by three points: (i) applied forces as
large as 10 mN were necessary to reveal all the softening transitions; (ii) mixtures 1 and
2 show two softening transitions, in the regions of - 10C and 70C; (iii) above a resin
component content of 50%, a single softening transition is observed; its characteristic
temperature increases linearly as the oil component content decreases.
The progressive loss of the oil of turpentine, which occurs with ageing, increases the
density of the structure and hardens the mixtures. This effect is taken as responsible for
point (i). Concerning point (ii) the hypothesis of a phase segregation process prevails
since the above-mentioned low- and high-temperature softening transitions corre-
spond to those of the oil and resin component respectively. Point (iii) is indicative of the
total consumption of the basic components of the mixtures in favour of the formation of
a stable mixed oil/resin phase.

4.3.4. Phase miscibility analysis

The above conclusions are in accordance with the observation, by eye, of the phase
miscibility of five-month naturally aged mixtures stored in capped quart bottles in the
dark at room temperature: phase segregation is confirmed in mixtures 1 and 2, while
mixtures 3-5 appear as dense, homogeneous gels.
Concerning the latter materials, it is suggested that the oil/resin interaction, what-
ever its nature, which insures the stability of the mixed phase, induces a distortion of the
original infrared signals from the basic components (shift, asymmetry, broadening)
which results at a certain stage in an apparent over-estimation of the carbonyl response
of the oil component. This effect is taken as responsible for points (ii) and (iii) in Section
4.2.3.

5. Conclusion

The suitability of a conjugated FTIR/TMA procedure to determine critical behav-

iour in naturally aged oil/resin mixtures was discussed on the basis of both a compara-
tive study with fresh mixtures of the same composition used as references, and a phase
miscibility analysis.
On the macroscopic scale, thermomechanical measurements clearly show non-linear
mechanical properties in fresh mixtures when the resin component content reaches the
value of 50%. In addition, a maximum in the hardness of the sample is observed for
a resin component content of 66%. These effects are attributed to the existence of an
effective oil/resin interaction, whatever its nature, which develops at the first stage of
mixing in materials with a resin component content above 50%. This interaction
appears to result in the long-term creation of a stable mixed oil/resin phase. A phase
miscibility analysis confirms these conclusions: phase segregation occurs in naturally
aged mixtures with a resin component content below 50%, while the other mixtures
appear as dense, homogeneous gels.
On the molecular scale, a simple quantitative infrared analysis was developed in the
carbonyl region with four Lorentzian functions. While the infrared responses of both
70 O. PagOs et al./Thermochimica Acta 287 (1996) 53-70

the oil and resin components are not affected by mixing in fresh materials, the above
procedure appears to be sensitive to the oil/resin interaction which holds the mixed
oil/resin phases: the latter induces a distortion of the infrared signals which results in an
apparent over-estimation of the carbonyl response of the oil component, with a maxi-
m u m for the resin component content of 66%.
The practical interest of this work is to demonstrate that natural paints made of
oil/resin mixtures with a resin component content below 50% develop phase segrega-
tion with time and are thus unstable in essence.
The physical significance of the critical resin component contents of 50% and 60%
will be investigated at the microscopic level in a subsequent contribution. This will be
realised through the combined analysis of the dielectric properties of conduc-
tor/insulator-like oil/resin mixtures by the thermally stimulated currents technique
(TSC) and low frequency dielectric spectroscopy (LFDS).

Acknowledgements

The research of O. Pag6s is supported by a grant from the European Union within
the scheme ' H u m a n Capital and Mobility'. The authors are very grateful to Katherine
Ara, Joyce Townsend and Steven Hackney, from the Tate Gallery, for providing test
samples and useful discussions on the background of the use of oil/resin mixtures for
paints.

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