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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.
58
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.
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.
60
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.
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.
61
Fig. 5. Homogeneity/dispersion control after extrusion. (1) Bad dispersion (two peaks); (2) good dispersion (one peak).
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)
Curing
Curing Impact
temperature time
D/R
(C)
(min)
(kg.cm)
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)
62
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
Fig. 7. Reactivity comparison. The same binder (EE) with two different catalysts.
63
Fig. 8. Check of the residual reactivity. (1) Uncured; (2) partially cured; (3) completely cured.
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).