Low Temperature Cure Strategies for Powder Coatings

Enric Grau and Montse Ballesteros (ARKEMA)

Powder Coatings have been a great advance for the coatings industry since their
appearance in the 70s. The advantages of low emission, high efficiency, reduced losses on
application, etc. enhanced their ecological behavior and their economic advantages. For
this reason, the studies and developments on better and more useful powder coatings
have been growing over the years. One of the research battle horses of the last years has
been the reduction of the cure temperature for two main reasons: Be able to cover
temperature sensitive surfaces and be more efficient with energy consumption. In this
article, we will explain the problems and our solutions developed in this issue.

Introduction
Since their invention, powder coatings have been adapting to the needs of the
coatings industry. For example, becoming more resistant to exterior exposure introducing
the polyester resins (combined with TGIC), maintaining an equilibrium between chemical
and exterior resistance with the hybrid system, improving the flow, making low gloss
paints, adapting to the new regulatory requirements and so on. However, despite all these
changes, powder coatings have always maintained their strengths:

 They are solvent free, therefore there are none or minimum organic volatile
emissions
 The overspray of powder is recoverable and reusable making the process
economic.
 Therefore, a less waste-disposal system produces less hazards making it more
environmentally friendly
 Finally, the system is very fast, compared to conventional liquid coatings and it can
produce thicker coatings without sagging, applying only one layer.
All these advantages produced a fast expansion and a growing market during
years. The first powder coating using thermosetting resin was an epoxy system, later the
hybrid system and finally the called “polyester” system that actually is a combination of
polyester on a high ratio (more than 90%) and a cross linker (TGIC, β-hydroxy alkyl amide,
Isocyanate, etc).
All of them need relatively high temperatures in order to cure. Some of them could
take advantage of a catalysis and others not. However, these temperatures are normally
between a range of 180 – 200 ºC, sometimes 160ºC. To reach lower temperatures we
 [Sidebar
need to overcome different obstacles depending on the particular system andTitle]
the kind of
application.
GRADIENT OVEN

A long steel panel is

EXTERIOR SYSTEMS inserted on the
If we want to cure a paint, intended to cover exterior opening. It will atbelow
elements
heated atwe
temperatures, for example, we will need to overcome two main problems: a need
gradient
to get
of temperature along
enough reactivity and we need to avoid the blooming phenomena that will appear when
their length for the
we cure at less than 160ºC.
time we have chosen
a) Reactivity to do the test.

For the first condition: reactivity, we should use a monomer composition and some
synthetic strategies in order to get enough reactivity. Fortunately, the Β-HYDROXY ALKYL
AMIDE starts its reaction at relatively low temperatures. The only problem is to reduce the
time it takes to reach a well-cured coating.
To know and compare the different reactivity of the resins we can use a gradient
oven. This type of oven is able to heat a long panel at different temperatures during the
test time we have chosen. As an example, we could heat the panel on a gradient of
temperatures starting at 120ºC and finishing at 185 ºC during the time, we want to
consider. Once we have made that, we could determine at which temperature the coating
cures in this time.

To determine if the coating has reached a full curing we can use the impact test. If
it is OK we can consider it has been well cured for this time / temperature value. To verify
this supposition, we have measured the Tg of the coating after testing it in the gradient
oven at different temperatures along the panel. The results are shown in the following
graph:
 Tg Evolution
Of a Coating exposed 15' at T
75

70

Reverse Impact OK
65
Tg (ºC)

60

55

50
125 130 135 140 145 150 155 160 165 170

PANEL T (ºC)

As you can see, there is a concordance between the maximum Tg, corresponding
to a well cured coating, and the good results on the impact test. Therefore, we can use
this criteria to know if the coating is cured.
Now we can do the test at three (or more) different times and get curing
temperatures for these times. We made three tests to obtain the minimum three points
to draw a curve. We can make this for every paint we want to compare and draw a graph
time/temperature.
The kinetics of the curing powder follows the Arrhenius equation that shows a
lineal tendency if the Y-axis is logarithmic. To verify the good behavior of the curve we
have obtained, we have presented the results choosing the time axis as a logarithmic one.
Here you can see the comparison of several powders:
However, to see the differences between paints it is better to show the same
graph using a normal Y-axis.
 Using normal axis you
TGIC - Cat KINETIC
Exponential (TGIC - Cat) could see that there are high
TGIC - No Cat. Exponential (TGIC - No Cat.) differences between curing
times at low temperatures.
100
Clearly, the TGIC system
needs to be more reactive to
finish the curing in a
reasonable amount of time.
TIME (min)

10
The Β-HYDROXY ALKYL AMIDE
system also needs to
increasing the reactivity but
not at the same level. To get
1
130 140 150 160 170 180 190 this increment on reactivity
TEMPERATURE (ºC) we have to perform some

KINETIC
TGIC - Cat Exponential (TGIC - Cat) TGIC - No Cat.
Exponential (TGIC - No Cat.) FAST PRIMID Exponential (FAST PRIMID)
SLOW PRIMID Exponential (SLOW PRIMID)
100

90 Low Temperature of Curing

80

70

60
TIME (min)

50

40

30

20

10

0
130 140 150 160 170 180 190

TEMPERATURE (ºC)

synthetic procedures but they should not compromise the good behavior of the paint.
b) Blooming
 Powder coatings formulated to coat exterior elements use resins with two
important monomer on their backbone: terephthalic acid (TPA) and neopentyl glycol
(NPG). The first one gives an excellent backbone to the structure of the resin and the
second one is the best selection to get a good exterior resistance. The problem of this
combination is that during the synthesis it is very difficult to avoid a common side reaction
between TPA and NPG that produces a cyclic molecule formed by two TPA and two NPG.
This molecule is very stable and it does not react to make other combinations. Therefore,
this substance remains in the polyester so that during melting and curing, it migrates to
the surface producing the blooming phenomena. Fortunately, the substance has a
sublimation point of about 157ºC and the blooming disappears when we cure at higher
temperatures (the most common situation). Anyway, once the coating is cured, we will
have the apparition of blooming after a very long lapse of time due to the slow migration
of the substance to the surface that happens even at room temperature.
In order to solve the blooming problem we need to avoid the reaction that
produces this molecule and, to do it, we need to produce a polymer using specific
synthetic procedures and/or a special monomeric combination. Moreover, we need to
take into account other needs like the reactivity and the exterior durability. All these
considerations make the problem like a puzzle of several pieces that have to combine
properly.
ARKEMA has designed the REAFREE 8563-T (and their equivalent for TGIC systems)
that meets all requirements. Here we show the blooming obtained once cured at a T
lower than 157ºC and after 1h at 140ºC. We have used a RAL 3016 formulation, dark
enough to see clearly the problem.

REAFREE 8563-T 665,0

Β-HYDROXY ALKYL AMINE 35,0

BENZOIN 3,0

BYK 360-P 12,0

YELLOW COLORTHERM 20 30,0

BAYFERROX 130 M 50,0

MONARCH 120 8,0

KRONOS 2160 1,0

BLANC ROC ULTRAMICRO 196,0

Cured at less than 157ºC
 On the graph we can see the level of blooming of the coating when is cured below
157ºC. Besides, the level of blooming of the same panel when we maintain it at 140ºC
during 1 h. That time at 140 ºC is more or less corresponding to several months at room
temperature. As you can see, there is no blooming when we cure the coating at a low
temperature using the special resin. After 1 h at 140ºC we get a high increment of
blooming using one standard resin and a slight increment using the special one.
c) Exterior Durability
The other factor we have to take into account is that the performance of the
coating must not to be affected by the synthesis procedures or the selection of monomers
we have used in order to get the non-blooming and the high reactivity effects. Therefore,
we have compared the special resin to a standard resin able to get GSB approval for
exterior. We have used the QUV-B test to do it (ISO 11507) and followed the GSB
indications. The results are shown in the following graph:

There is an acceptable weathering resistance for an exterior coating using the new
special resin. Other properties, like impact test, gloss, etc. are ok.
INTERIOR SYSTEMS: Ultra Low Bake Hybrid System
Interior systems do not require a very good exterior resistance. Therefore, we
could use a linear epoxy as cross linker. The standard ratios between polyester and epoxy
varies from 70:30 to 50:50. Anyway, if we go for a high reactivity system we will chose the
50:50 option to get the coating cured at 130-140ºC for 15 – 20 minutes, the so-called
ultra-low bake curing.
There are two reasons to use a paint able to cure at low temperatures. To reduce
the energy consumption and to cover temperature sensitive substrates. The standard
temperatures to cure powder coatings: 160 – 200ºC, are too high for some substrates like
wood or plastic. The good thing is that we usually have these substrates on interior
stances and we can use the hybrid system to make the paints.
Get a hybrid system with sufficient reactivity to cure 130 - 140 is only part of the
problem. The hard part is doing it getting good leveling and good appearance. We will
have to fight many problems: degassing, adhesion, and every imaginable surface defect.
To solve all these non-desired effects we have to work on two sides: the composition and
synthesis of the resin and the formulation of the powder coating. Nevertheless, previously
we have to consider some issues derived from the substrate.
a) Substrate Problems: Conductivity and Degassing
The first issue is the conductivity. With metallic surfaces, we do not have a big
problem but using wood, plastic or the like, we will have to improve their conductivity. To
cover a wooden material, for example, we could take advantage of the hygroscopic nature
of wood (humidity increases conductivity) but this goes against the formation of the film
(water evaporates during the curing process leading to degasification problems). We have
two ways to solve the problem:
- We can cover the substrate with a first conductive layer of a liquid coating. This
might work well and can improve the leveling of the final coating. However, it
has the disadvantage of applying two layers. In addition, we have to use two
different technologies.
- And other option, more interesting, is to use a type of wooden substrate with
some level of conductivity.
Following this second idea, one could consider to applying the paint directly over a
piece of natural wood. However, we are at risk to obtain a bad appearance. Some bases,
such as tropical woods, should be rejected because of their high content of fatty
substances and exudates and their narrow, winding pores. The nature of these exudates
and extracts are complex products (colourings, essential oils, waxes, fats, resins and tannic
substances) which can flush up irregularly on the surface, creating problems with the
application of decorative or protective coatings impossible to solve with additives.
 The optimum solution is Medium Density Fibreboard (MDF). This is a board made
with fibres of wood agglutinated with synthetic resins using high pressure and heat, and
dried until a medium density is achieved. To make it hydrophobic, paraffin is added during
the production process. It is worked in practically the same way as solid wood, and it can
be fully milled and cut. The dimensional stability, unlike solid wood, is optimum. It makes
an excellent base for wooden veneers.

b) Good Leveling
On the particular case of a wooden material, the major problem is wood’s thermal
conductivity as well as the negative effect of heat on it. However, when decreasing the
temperature the product’s extensibility also decreases, thus creating an irregular-looking
surface, which is a problem for an industry where appearance is an important added
value. When we are baking at 130 - 140 º C using an amorphous resin, for example, we
will have a high viscosity during the film formation than results in bad leveling. To avoid
the problem and reduce the viscosity we will use a monomer composition that is likely to
decrease the glass transition temperature, so we will reduce the storage temperature. It is
important to achieve a good balance between storage conditions and good leveling and
this is achieved not only by using a suitable resin but also with suitable additives on the
paint formulation.
The other variable is the reactivity. Or, in other words, the time we gave to the
coating to flow. As you can see on the following graph, there is a direct relation between
the reactivity, expressed as gel time, and the flow, expressed as pill flow.

As the level of reactivity is fixed to get the needed cycle time/Temperature to cure
the paint, the only variables left to modify are:
- Resin design
- Paint Formulation
On the first variable, the resin, we could reduce the viscosity to improve the flow
working on their synthesis design. Therefore, we will get a low melting viscosity taking
advantage of the short time before curing. However, this certainly is going to go against
storage stability (reducing glass transition temperature, Tg). We have to reach a good
compromise between flow and Tg. We have designed several resins able to do this work.
Here we have taken the REAFREE 6841 as a good example of ultra-low bake resin, able to
cure at 130-140ºC, and getting an excellent equilibrium between flow and Tg.
Once we are working with the best possible resin, the next step is to work on the
formulation of the paint. More specifically, playing with the additives we can put in it.
 Pill Flow vs Gel Time
Different Gel Time due to Diferent Resin
35 Reactivity
33
31
29
27
25
Pill Flow (mm)

23
21
19
17
15
200 250 300 350 400 450

Gel Time (s)

Formulation and Additives for an Ultra-Low Bake Paint
There are two main additives to consider getting two different effects:
- Reduce viscosity
- Improve degassing
For the first effect, reduce the viscosity and improve the flow, we recommend
CRAYVALLAC PC. It has also some effect on degassing.
For the second effect, the best option is CRAYVALLAC WN-1265. It extremely
improves the degassing of powder paints.
Following you can see a graph showing the effect on pill flow and Tg of these
additives. You can see on the first point the values for a paint with no additives; on the
second point the values for a paint with only CRAYVALLAC PC and, finally, the third point
with the values of a paint with the two additives.
 Crayvallac InfluencePaint Tg
Pill Flow
Paints of same Catalyst Level
70 18

16
60
14
50
12
40 10

30 8
Paint Tg (ºC)

Pill Flow (mm)

6
20
4
10
2

0 0
No additives PC PC + WN-1265
PAINTS

As you can see, the reduction of Tg is very small and justified for the high Flow
improvement. To see the need of degassing additives on this paint, we show here a graph
exposing the efficiency of the wax improving the degassing limit over a substrate with
some level of emissions (exudates, water, etc.).
 DEGASSING LIMIT
160

140

120

100
Degassing Limit (film thicness in um)

80

60

40

20

0
0 0.5 1 1.5 2 2.5 3 3.5 4

WAX (%)

To conclude we propose here one formulation as an example that, following all the
previous considerations, has a very good performance on ultra-low bake systems.
REAFREE 6841 330,0
ARALDIT GT-7004 330,0
CRAYVALLAC PC 10,0
CRAYVALLAC WN-1265 10,0
Benzoin 5,0
BYK 360-P 10,0
TiO2 (KRONOS 2160) 305,0
TOTAL 1000,0
Conclusions
We have exposed here a few ideas to meet the challenge of curing at low
temperatures and some of our contributions in this field in the form of resins and
additives. To resume, we say:

 For powder coatings used on exterior elements we need:

o Enough reactivity to cure at low temperature
o Avoid the blooming problem
o Meet all the requirements for a paint used on exterior (QUALICOAT, GSB)

Our solution to this is REAFREE 8563-T using a standard formulation for exterior
conditions

 For powder coatings used on interior elements we need:

o Enough reactivity to cure at very low temperature
o Avoid the leveling problems produced due to high viscosity at these
temperatures
o Avoid the degassing problems produced by some substrates

Our solution is REAFREE 6841, using a special formulation with the additives:
o CRAYVALLAC PC (leveling)
o CRAYVALLAC WN-1265 (degassing)