Progress in Organic Coatings 34 (1998) 5763

Powder coatings and differential scanning calorimetry: the perfect fit

Luigi Gherlone*, Tullio Rossini, Vladimir Stula
Akzo Nobel Coatings, Italy, Viale Matteotti, 39-22012 Cernobbio, Como, Italy
Received 15 July 1997; revised version received 11 September 1997; accepted 19 May 1998

Abstract
A thermosetting powder coating is the ideal field of application for differential scanning calorimetry (DSC) analysis. A review of the
existing techniques is done and a new product characterization approach is discussed in comparison with some traditional methods. Time
savings, effectiveness and compliance with the objectives, can be advantageously obtained by using DSC analysis versus alternative
methods (gel time, solvent cure test, storage stability, mechanical test, etc.). An attempt is made to provide a quick one shot analytical test
to predict storage stability, curing behaviour, processing conditions and in some way the end-use performance of powder coatings. 1998
Elsevier Science S.A. All rights reserved
Keywords: Powder coatings; Cross-linking; Glass transition temperature; Differential scanning calorimetry; Storage stability

1. Introduction
Differential scanning calorimetry (DSC) is an analytical
discipline well established and widely used since the early
seventies.
A DSC instrument consists of a kind of twin calorimeter,
served by a computerized proper software where possible to
measure the heat flow of a sample as a function of temperature.
This allows one to obtain information on heat evolution
or absorption and, specifically referring to a paint, to investigate cross-linking reactions, solvent and other material
release, glass transition, etc.
Here problems and misinterpretations can arise when
superimposition of different events, with positive and negative heat flow, occur simultaneously as with exothermal
cross-linking and endothermal release of material.
It can be concluded that DSC is hardly applicable for
general investigation and characterization of liquid paint
systems where solvent evaporation and unsuitable crosslinking reactions (e.g. polycondensation) affect the thermal
analytical response.
In the case of powder coatings no solvent is involved and,
what is more, most of the cross-linking systems are based on
* Corresponding author.

0300-9440/98/$19.00 1998 Elsevier Science S.A. All rights reserved

PII S0300-9440 (98 )0 0039-3

polyaddition reactions with consequent no emission affecting the analytical result.

A world-wide production of 550 000 tons for thermosetting powder coatings was estimated in 1997.
The split according to the chemical nature of the binder
gives more than 80% of the production based on polyaddition chemistry [1].
If we refer to the European figures the total of epoxy,
epoxy/polyester (hybrids) and polyester/TGIC powders
(all systems cross-linking by polyaddition) accounts for
more than 90% [2].
All these types of powders can be considered the ideal
subject for a quick and useful characterization by DCS.
Fig. 1 is a typical DSC plot of a thermosetting material.
The first event encountered is the glass transition temperature (Tg), shown by a sudden increase of the specific
heat.
The Tg, definable as the temperature at which an amorphous material changes from a glassy to a soft or rubbery
state, is correlated with the softening point of the material.
Coming forward through the diagram, we can note the
starting of an exothermic reaction, showing that the crosslinking is taking place. The area under this peak represents
the enthalpy of the cross-linking reaction. Fig. 2 presents a
detailed picture.
The Tg (43.8C) can be considered a kind of softening

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L. Gherlone et al. / Progress in Organic Coatings 34 (1998) 5763

Fig. 1. Typical DSC diagram of a thermosetting material.

point of the system and thus can be related to the storage

stability of the powder.
It may be advisable to remind that the coating powders
storage instability is not generally induced by chemical
reactions but is simply due to the physical softening and
consequent sticking together of the particles.
The result of the above condition is a bad or absent freeflowing, resulting in a difficult or impossible application of
the powder.
The area under the peak of Fig. 2 is expressed in units of

energy and, for a given reaction, is directly proportional to

the amount of cross-linking which has taken place.
The area and temperature profile indicates the effectiveness of curing agents, accelerators, and so on.
This shows that a single DSC experiment can reveal, in
less than 1 h, the basic behaviour of the curing reaction and
the storage stability. But there is more!
Considering the rerun after cooling of the same sample
(the broken line curve in Fig. 2), the Tg of the cured film is
obtained.

Fig. 2. DSC diagram of an epoxy powder coating.

L. Gherlone et al. / Progress in Organic Coatings 34 (1998) 5763

This important parameter is frequently undervalued and

not always used, probably because of the unavailability of
reliable data correlating Tg and the final performance of a
coating film.

2. Testing scenario
A large majority of thermosetting coating powders have a
Tg between 40 and 60C, a melting interval between 80 and
100C and a curing temperature between 130 and 200C.
Based on previous experience the following operating
conditions were chosen: DSC7 instrument (Perkin
Elmer), sample weight 1525 mg (minimum 4 mg), heating
from 20 to 280C, scanning rate 10C/min.
For a precise determination of Tg.

Heating from 20 to 100C, scanning rate 10C/min

(a strong hysteresis peak is usually present, which
makes the evaluation difficult).
Cooling from 100 to 20C, scanning rate 10C/min.
Heating from 20 to 100C, scanning rate 10C/min.

In some cases, further measurements had to be done at a

scanning rate of 25C/min.
For special applications (e.g. evaluation of curing conditions), isothermal analysis at specific temperature could be
preferable to working with a temperature gradient.
Some typical examples of use of DSC analysis for powder
coatings, in R&D and in QC are presented.

59

3. Storage stability
As previously mentioned, the storage stability of coating
powders is normally tested by keeping powder samples in
the oven at a determined temperature (3050C) and by
observing if the powder maintains free-flow properties or
starts caking or blocking.
Determination of Tg of the coating powder is much
quicker and more precise.
We are using it successfully in development of new products and in QC.

4. Some brief case histories

A standard epoxypolyester powder, currently used in
north Italian market, showed transport and application problems (caking, agglomerates, bad free-flow, etc.) if sent to
hot countries.
A new formulation, having better storage stability, has
been quickly developed: more suitable raw materials with
higher Tg were selected, experimental powders were prepared and tested following the indication reported in Fig. 3.
Some coating powders showed caking problems during
and after transport in the summer season, particularly if they
were shipped immediately after production.
It was possible to prove by DSC analysis that the freshly
produced powder had a much lower Tg than the same product stored at least 24 h at 2030C: Tg continued to

Fig. 3. Variation of Tg in an epoxy-polyester powder by changing the type of epoxy resin.

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L. Gherlone et al. / Progress in Organic Coatings 34 (1998) 5763

Fig. 4. Variation of Tg during storage. (1) Freshly produced powder; (2) after 24 h storage at 30C; (3) after 3 months; (4) after 1 year.

increase and reached a maximum value only after 36

months (Fig. 4).
This phenomenon can be explained by reassessment of
the binder (rearrangement of macromolecular segments).
The caking problem could be solved by keeping the
freshly produced powder for at least 1 day in a cool place.

5. Quality control.
The storage stability of the coating powder depends not
only on the binder but also on additives and general formulation, and also on the particle size distribution (finer powders can have lower storage stability than coarser ones). It is
therefore necessary to find experimentally, for every group
of products, a correlation between Tg and an effective storage stability.
For some important applications, we had to introduce Tg
into the product specifications and use it as a routine test
method. It is also regularly checked in QC of some critical
raw material.

6. Chemical storage stability

Some fast curing coating powders can pre-react after a
prolonged storage, even at room temperature. Consequently, the properties of the coatings would deteriorate
(loss of flow, decreasing of mechanical properties, etc.).
The chemical storage stability can be well studied by
repeated DSC analysis of samples stored at different temperatures and by comparing their Tg and reaction kinetics.

Accelerated testing is possible by ageing of the powder

sample by isothermal run in the DSC apparatus.

7. Homogeneity of the extruded product

Coating powders are usually produced by premixing of
all the raw material, followed by extrusion, grinding, sieving and packaging.
To obtain a high quality product, a very good homogeneity and high degree of dispersion must be reached. It is
therefore necessary to optimize the extrusion process (type,
length and pattern of the extruder, extrusion temperature,
speed and throughput are some variable parameters).
It is often possible to check the degree of dispersion by
evaluating of the DSC curve: if Tg of the single organic
components (resins, hardeners, additives) is significantly
different (at least 510C) and the dispersion is bad, there
will be multiple peaks in the area of glass transition temperature; a homogeneous product has a clear single Tg (Fig. 5).
However only this is true if the single components are
compatible. The Tg of incompatible components would
remain separate; additives used in small quantities cannot
be detected in this way [3].

8. Determination of curing conditions

Determining of minimum curing time at different temperatures is normally done by testing mechanical properties
and/or of solvent resistance on coated panels, cured with
different curing schedules. A single DSC analysis allows

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L. Gherlone et al. / Progress in Organic Coatings 34 (1998) 5763

Fig. 5. Homogeneity/dispersion control after extrusion. (1) Bad dispersion (two peaks); (2) good dispersion (one peak).

one to obtain more detailed and quick information. In Fig. 2

a printout of the kinetic parameters appears.
According to the Arrhenius theory, the kinetic data can be
used to predict the behaviour of the reaction under isothermal conditions at various temperatures.
The complete validity of the Arrhenius theory for all the
reactions involved may be criticized, nevertheless practical
correlation and usage have been found.
In Table 1 the typical pattern of isothermal analysis split
in a wide range of temperature is presented.
This kind of table proved to be reliable when changing
from the currently used stoving schedules (15 min 190C)
to the peculiar ones of can and coil coating (1 min
230C).
There is a good correlation between the curing times
calculated from DSC data and those found by evaluation
of mechanical properties and solvent curing test (Table 2).
Table 1
Isothermal split out of an epoxypolyester powder coating curing reaction
peak
Temperature
(C)

Conversion
%

Isothermal analysis
180.00
97.00
200.00
97.00
220.00
97.00
240.00
97.00
260.00
97.00
280.00
97.00
300.00
97.00

ln (k)
(s1)

P(0)
(W/kg)

Time (min)
15.78
8.45
4.76
2.80
1.71
1.09
42.91

5.59
4.97
4.40
3.87
3.38
2.92
2.50

135.54
253.15
449.45
763.03
1244.96
1960.63
2991.38

It is however necessary to find experimentally for each binder the percentage of conversion necessary for reaching
maximum mechanical properties and solvent resistance.
Table 2
Correlation between the curing times calculated from DSC data and those
found by evaluation of mechanical properties
Curing of coated panels
in lab oven (object T)

DSC isothermal analysis

Curing
Curing Impact
temperature time
D/R
(C)
(min)
(kg.cm)

Temperature Conversion Time

(C)
(%)
(min)

180
180
180
180
180
200
200
200
200
200
220
220
220
220
240
240
240
240
260
260
260

180
180
180
180

92
95
97
99

11.4
13.5
15.8
20.8

200
200
200
200

92
95
97
99

6.1
7.2
8.5
11.1

220
220
220
220

92
95
97
99

3.4
4.1
4.8
6.3

240
240

95
97

2.4
2.8

260
260
260
260

92
95
97
99

1.2
1.5
1.7
2.3

8
10
12
14
16
5
6
7
8
9
3
4
4.5
5
1.5
2
2.5
3
1
1.5
2

10/0
20/5
35/10
60/10
80/80
5/0
30/10
60/35
80/60
80/80
10/0
50/30
70/50
80/80
5/0
20/5
50/30
80/80
0/0
40/20
80/80

(max)

(max)

(max)

(max)

(max)

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L. Gherlone et al. / Progress in Organic Coatings 34 (1998) 5763

Fig. 6. Reactivity comparison. (1) Without catalyst; (2) 0.15% catalyst; (3) 0.3% catalyst.

9. Reactivity
DSC analysis is very useful to evaluate the behaviour of
different potential reaction catalysts and accelerators. It
serves also to check if some additives have or not any secondary accelerating or retarding effect.
You can see (Figs. 6 and 7) from the DSC curve (and
from the isothermal analysis), at which temperature the

cross-linking reaction starts and ends and how the reaction

enthalpy changes. From these data not only the obtainable
curing condition but also the foreseen effect on appearance of the coating can be predicted, (e.g. a latent accelerator, which does not decrease the T at which the
reaction starts, but reduces the T at which it ends,
would allow faster curing without decreasing the levelling
of the coating).

Fig. 7. Reactivity comparison. The same binder (EE) with two different catalysts.

L. Gherlone et al. / Progress in Organic Coatings 34 (1998) 5763

63

Fig. 8. Check of the residual reactivity. (1) Uncured; (2) partially cured; (3) completely cured.

This can speed up the choice of the best suitable catalyst

and its correct concentration in the formulation.

10. Checking of full/incomplete curing

It is sometimes difficult to prove that a failure of a coating
(e.g. insufficient mechanical properties or low solvent resistance) was due to incorrect curing (any problem with the
curing oven) and not to the quality of the coating powder.
DSC analysis can be very useful in such cases.
It is possible to check the degree of curing by the residual
exothermal (Fig. 8). A DSC analysis is made on a reference
fresh coating powder to obtain a value of the total specific
enthalpy of the reaction (J/g). Then an analysis of a sample
of the cured coating is carried out. If it was completely
cured, the exothermal peak will completely disappear; if
the curing was not complete, there will be a residual
exothermal reaction; the residual specific enthalpy is proportional to the degree of incomplete curing (undercuring)
[4].
Insufficient curing can also be revealed by DSC in other
ways:

checking the Tg as a function of curing time or

temperature [5];
via isothermal analysis [5,6].

11. Conclusions
DSC has proved to be a valuable tool in designing, formulating and testing of powder coating.
Storage stability and curing behaviour can be predicted
via quick and simple tests.
DSC has proved useful also in quality control of the process and raw material.

References
[1] UATCM Eurocoat 96, Vol. II, 1820 September, 1996, p. 532.
[2] UATCM Eurocoat 96, Vol. II, 1820 September, 1996, p. 521.
[3] S.W. Shalaby, H.E. Bair, Thermal Characterization of Polymeric
Materials, Academic Press, New York, 1981, pp. 365428.
[4] C.M. Neag, in J.V. Koleske (ed.), Testing Manual: Gardner-Sward
Handbook, 14th ed., ASTM, Philadelphia, PA, 1995, p. 862.
[5] A.P. Gray, PerkinElmer TAAS-2 (1972).
[6] B. Cassel, PerkinElmer TAAS-19 (1977).