Understanding Benzoin in Powder Coatings

Use of powder coatings is growing rapidly. However, surface defects such as orange peel and
pinholing prevent the expansion of powder coatings into some markets. For the prevention of
pinholes due to degassing, benzoin has been the favorite material because of its high
efficiency and low cost. In fact, benzoin is used in virtually all powder coating systems
worldwide. The prospect of developing an improved air-release agent has stimulated research
on benzoin's role in degassing in powder coatings. In some cases, alternative air-release
agents have been developed, but these alternatives generally fall short either in performance
or in terms of economics.

Figure 1: Effect of Benzoin Level on Curing of Epoxy

Despite the fact that benzoin has been used for more than 20 years as an additive in powder
coatings for the reduction or prevention of pinholing, its precise mode of action is still
unknown. Explaining how benzoin aids in the release of air and volatiles from the various
powder systems is a necessary step along the way to designing benzoin replacements that will
overcome its deficiencies. The investigation described in this paper attempts to answer
questions about the fate of benzoin during cure, its effect on melt viscosity and cure profile,
and the kinetics of devolatilization of the powder during the cure cycle. This paper is adapted
from work originally presented at the 2000 Athens Conference (1).

Background
Over the years, a number of patent applications on benzoin substitutes have been filed. For
example, an application filed in 1976 by Jiro Yoshikawa at Nippon Paint Co. claims a number
of compounds, including bisphenol A, phenyl acetylsalicylate and benzoin, that prevent
foaming in epoxy-based powder coatings (2).

In 1992, Jan Schippers at DSM filed a patent application claiming that crystalline waxes
could be used to prevent pinholes without yellowing in Primid-based systems (3). This
application claims that some crystalline waxes will prevent pinholes while avoiding the
yellowing seen during curing in Primid systems with benzoin, especially under overbake
conditions. Also in 1992, a patent by Stanislaw Skora claims a bisphenoxy propanol
compound that can completely prevent pinholes in thermosetting powders when used at
levels of 0.5 to 3% by weight (4). In a paper presented at the Waterborne, Higher-Solids and
Powder Coating Symposium in 1993, William Arendt of Velsicol claims that 1,4-cyclohexane
dimethanol dibenzoate (CHDM Dibenzoate) gave excellent coatings with less yellowing at
levels three to nine times higher than that of benzoin in epoxy-hybrid systems (5). In a
European patent application filed in 1993, Wilkinson and Phillips claim a solid thermoplastic
polymer can be used in place of benzoin in Primid-based powder coatings to give superior
color. The use of these solid thermoplastic degassing agents in other powder systems is
mentioned with statement to the effect that differences in color are noted in other systems.
This application is the first to attempt to explain how degassing or air-release agents work.
The authors claim degassing agents have a surface tension effect that "holds the surface
open" during cure (6). However, no data is offered to support the claim.
In the past decade, there have been several studies to learn the mechanism of air release. For
example, Randoux, et.al., showed that benzoin and benzil, a bright yellow oxidation product
of benzoin, are evolved from the coating during cure in a variety of powder coating systems
(7). Uhlmann reported that benzoin reduces wetting tension in epoxy systems while having a
slight effect on melt viscosity and Tg (8). Uhlmann also reports that a high MW butyl
acrylate flow modifier is more efficient than benzoin in reducing wetting tension.
Furthermore, benzoin provided no additional reduction of wetting tension when used with a
flow modifier. The fact that benzoin does not add to the effect of the flow modifier on wetting
tension suggests that wetting tension is not a major factor in air release. The presence of
benzil as an impurity in benzoin is often cited as the source of the yellowness found in
powders formulated with benzoin. Uhlmann suggests that the amount of benzil in benzoin is
important because benzil has a significant influence on the effect of benzoin during film
formation. He also states that it is important for manufacturers to realize that storage
conditions for benzoin may affect the benzil content and thus affect the air-releasing
properties of the benzoin. It is also stated that the quality of the coating is dependent on the
fact that benzil can leave the coating while benzoin remains in it. This statement contradicts
the work of Randoux cited above.

While significant attempts had been made to determine how benzoin promotes gas release
and prevents pinhole formation during powder coating curing, no clear picture emerges as to
why benzoin is so effective. In addition, no cost-effective replacements for benzoin have been
forthcoming in the last 25 years of powder coating development. Clearly, a better
understanding of how benzoin works might help to develop a new generation of gas-release
agents that do not yellow during cure. This paper describes our work to develop such an
understanding.

Table 1

The Experiment
Initially, the work focused on the effect of benzoin on the rheology and cure profile of the
coating. A clear epoxy system was selected as a good model for these studies (Table I).
Samples containing varying amounts of benzoin were subjected to dynamic mechanical
analysis (DMA), gel-time determination, inclined plate flow, TGA, photoacoustic IR,
attenuated total reflectance (ATR) IR and headspace GC analysis.
The gel-time test was repeated in an epoxy-hybrid system (Table 1) and a polyester/blockedisocyanate system to determine if the effects seen in the epoxy system were reproduced in
other cure systems.
Typical powder formulation conditions were as follows: The components were mixed on a
roll mill in 0.5-gallon jars for one to two hours. The mixed components were then extruded
on a Buss PCS-30 single-screw extruder at 300 rpm. The extrusion temperatures were 100C
for the epoxy and epoxy-hybrid systems and 130C for the polyester/blocked-isocyanate
system. The extruded samples were pulverized on a Retsch ZM-1 hammer mill to pass a 0.5mm sieve. The ground powder was then passed through a 200-mesh screen before spraying
using a Gema PG-1 corona spray gun on either Q-Panel 0.025- by 3- by 6-inch aluminum or

0.025- by 3- by 6-inch steel panels. The panels were cured for 10 to 15 minutes at 180C for
the epoxy and epoxy-hybrid samples and for 15 minutes at 204C for the polyester/blockedisocyanate system.

Results and Discussion

Rheology and Cure Rate. Benzoin is known to lower the melt viscosity and the surface
tension of powder coatings (8,9). Benzoin's effect on melt viscosity was seen in our studies as
well (Figure 1). However, the magnitude of the viscosity change is small and is negligible at
the low concentrations of benzoin used in commercial practice. The reduction of the surface
tension of the coatings alone cannot account for benzoin's effectiveness as an air release agent
because other additives are more effective at reducing surface tension but are less effective as
air-release agents. For example, flow modifiers are very effective at reducing surface tension
but are not very effective at reducing pinholes.

Figure 2: Attenuated Total Reflection IR Spectrum of Partially Cured Epoxy Pane

The gel-time studies confirmed that benzoin delays the cure in epoxy systems by 30% and in
epoxy-hybrid systems by 13 to 14%. However, in polyester/blocked-isocyanate systems, the
effect on the cure rate of the resin was small (ca. 6%) and statistically questionable. Given
that benzoin is effective in all three systems but has a much different effect on gel times in the
three systems, it seems unlikely that the delay of cure is the mechanism of the air release
process. While benzoin definitely affects the rheology and the cure rate of powder coating
formulations, the evidence does not support the conclusion that these effects alone account
for benzoin's effectiveness as an air release agent.

Volatiles. Another possible explanation for benzoin's effectiveness is its volatility, i.e. it
rapidly migrates to the surface of the coating and vaporizes carrying along other volatiles
with it. Benzoin would, in effect, open a path for other volatiles, increasing the flux of gas
leaving the coating. In support of this theory, it has been shown that benzoin sublimes from
coatings during cure (7). However, it is not known how much of the benzoin leaves the
coating or when the exodus occurs during the curing process.
To quantify the amount of benzoin that leaves the coating during cure, a series of samples
containing varying amounts of benzoin were subjected to headspace gas chromatography
(GC) analysis. For this test, a known quantity of clear epoxy powder was weighed into a
sealed sample vial that was then heated to 180C for 15 minutes to simulate a cure. The
headspace of the sample container was then sampled and subjected to GC/MS to determine
the amount and composition of the volatiles evolved.
The results of this study are surprising. It was expected that benzoin would be seen in
substantial quantities, perhaps as high as 50% of the benzoin in the coating. Instead, it was
found only in a minute amount in the sample containing 5 weight-percent benzoin. Both
benzaldehyde and benzoic acid were found in the headspace, but at levels that indicate that
the majority of benzoin stays in the coating. There are reasons to doubt this conclusion. First,
the coating in the vial is very thick for a powder coating (ca. 5 mm). As a result, diffusion of
benzoin to the surface would take substantially longer than in a typical coating of 70 mm.
Another reason is that the photoacoustic IR spectrum of a cured panel could not find any
trace of benzoin in the coating and the TGA/MS analysis of the coatings reveals that benzoin
does indeed leave the coating.
Benzoin in the Coating. Photoacoustic IR was used to scan cured panels that had been
sprayed with epoxy powder paint containing 0, 0.5, 1.2 and 5 weight-percent benzoin. An
authentic sample of benzoin was used for a reference spectrum. Comparison of all four
samples at 200 Hz shows none of the distinct benzoin bands, even in the sample containing 5
weight-percent benzoin. There appears to be no detectable amount of benzoin in these cured
panels. This result conflicts with the headspace GC results. In order to resolve this conflict,
additional testing was carried out.
Dynamics of Benzoin. Thus far, the testing has primarily looked at coatings after the cure is
complete. If the benzoin does sublime, oxidize or degrade, it is a dynamic process that starts
as the coating melts and coalesces and ends upon complete gelation of the coating or when all

of the benzoin has been consumed or vaporized. In an attempt to look at the dynamics of the
curing process, panels were sprayed with the epoxy clearcoat formulation containing either 0,
0.5 or 1.0 weight-percent benzoin. These panels were then cured at two-minute intervals from
two to 14 minutes at 180C. The resulting panels were analyzed by ATR IR (Figure 2) and
Photoacoustic IR (Figure 3). The results indicate that benzoin disappears rapidly during cure.
In Figure 2, a significant peak is seen at 1559 cm-1, which diminishes quickly. By eight
minutes, there are no longer traces of the benzoin absorbances. A depth analysis indicates that
benzoin is concentrated near the surface (Figure 3). The curve at 800 Hz is essentially on top
of the curve at 400 Hz in the region of the benzoin absorbance at 1559 cm-1. While not
conclusive, this work suggests that benzoin migrates to the surface and then disappears
during the first six to eight minutes of cure.
Thermal Gravimetric Analysis/Mass Spectroscopy (TGA/MS). To quantify the amount of
benzoin and other volatile components that leave the coating, TGA/MS was performed on
samples containing different levels of benzoin. The TGA/MS was able to track volatiles
evolving from the coating and identify them. Originally, all samples were thermally scanned
from 50 to 300C at 20C per minute. By this technique, it was seen that between 150 and
250C, the only volatiles seen in the control containing 0% benzoin were decomposition
products of the amine curing agent for the epoxy coating. In the samples containing benzoin,
mass loss attributable to benzoin (mass peaks at 105 and 77) were found. Furthermore, the
mass loss attributable to benzoin occurred between 180 to 250C, which is within the powder
curing-temperature range.
In each case, it was benzil, not benzoin, that evolved from the coating. Further examination
of the equipment set up suggests that the benzil results from oxidation of benzoin in the
transfer tubing after it leaves the coating. This was confirmed by evaluating the volatiles from
direct insertion of the coating sample into a mass spectrometer. Upon direct insertion, one
sees benzoin in the volatile stream. As a result of this finding, it is not possible to determine if
benzoin is oxidized to benzil in the coating.
Unfortunately, the amount of mass lost as benzoin or benzil could not be precisely measured
due to the small amounts involved. In samples containing 5% benzoin, it appeared that about
half of the benzoin left the coating, but this needs to be confirmed by another study.
To determine when the benzoin evolves from the coating, an isothermal experiment was
conducted. A sample containing 5% benzoin was rapidly heated to 190C over a four-minute

period and then held at 190C. Mass loss started as the temperature reached approximately
125C and proceeded rapidly. The benzil (attributed to benzoin) evolved over a six- or sevenminute period. This result agrees very well with the finding from the photoacoustic and ATR
IR studies reported earlier that benzoin disappears from the coating during the first six to
eight minutes of cure.
Optical Microscopy. While trying to determine what was happening to benzoin in the
coating, we also wanted to find out what was happening to the coating itself. A method was
developed to examine a powder coating as it cured on a hot-stage microscope. Thin glass
slides were sputter-coated with a thin layer of Pd/Au metal to provide a conductive surface
that was optically transparent (20- thick). These slides were then sprayed with a clear epoxy
powder using an electrostatic spray gun. The resulting powder coated slides were inserted
into a hot-stage microscope oven and heated to 200C as quickly as possible. The curing of
the coating was recorded on videotape as a function of time. These videos dramatically show
the effect of benzoin on the air, water vapor and other volatiles trapped in the melting coating.
The still photos (Series 1,2,3) illustrate the important points:

Figure 3: Photoacoustic IR of Clear Epoxy (1% Benzoin, Cured: 2 min @ 180C)

Series 1 shows the melting, coalescence and flow part of the cure process for a clear epoxy
powder containing 0.5% benzoin. Photo 1, shows the loose powder is electrostatically
attracted to the slide with light passing up through the particles. Less than 40 seconds later, in
Photo 2, the particles have melted and are coalescing, but flow and leveling have not
occurred. Flow and leveling are nearing completion in photo 3 and a multitude of small

bubbles are seen. At this point, the curing process is 45 seconds old. The photos in Series 2 &
3 begin after melting and flow and leveling are complete but before the trapped gas bubbles
have escaped. These trapped gas bubbles are believed to be composed mostly of air, with
some water vapor and a small amount of volatiles from the coating.

Series 1
Series 2 is a clear epoxy containing no air-release agent (no benzoin). Examine the top pair of
photos first. The left shows the coating immediately after melting, coalescence and flow have
occurred. There are thousands of bubbles of trapped gas of differing sizes. On the right, the
picture shows the coating about 45 seconds later. In this photo, there are fewer bubbles, and
careful examination shows that the remaining bubbles are smaller. In photo 3, the time is
about one minute, 45 seconds after the second photo or about two and a half minutes into
cure. The bubbles have shrunk a small amount, and there are fewer bubbles. In photo 4, the
bubbles look the same, and the time is about five minutes into the cure. By this time, the
curing process has progressed to the point where diffusion of the gas through the coating is so
slow that no further changes are noted, even after 15 minutes.

It was originally thought that the bubbles would rise to the surface and burst, but this does not
occur. Instead, the bubbles shrink in place due to the gas permeating the polymer matrix. The
pinholes appear to be a result of the collapse of these bubbles as the coatings cool. More work
is needed to correlate the sites of large bubbles with pinholes in the final cooled coating.
The epoxy clearcoat with 0.5% benzoin added in Series 3 shows a dramatic difference.
Initially in photo 1, the scene is much the same as in Series 2. However, it is apparent in
photos 2, 3 and 4 that the bubbles shrink and disappear rapidly over the course of roughly
four minutes. The circles are included to help compare individual bubbles to see the
shrinkage. Note that by photo 4, virtually all of the gas has escaped from the coating
containing benzoin.

Conclusion
This work has clearly shown that benzoin escapes from the coating in the first six to eight
minutes of cure, and during that same period of time, the gases trapped in the coating during
melting and coalescence also escape. This finding, more than any other, offers the first real
glimpse of benzoin's mode of action. While benzoin has been shown to affect the rheology,
surface energy and cure response of powder coating systems, none of these factors alone
could explain its unique effectiveness. However, the volatility of benzoin, perhaps in
combination with those effects, provides the opportunity for the gases to escape. The release
of the gases from the coating is a function of the coatings permeability. The bubbles do not
rise to the surface and burst. Instead, they shrink as the gases inside diffuse and/or dissolve in
the coating matrix. The benzoin facilitates this process by increasing the permeability of the
coating. Whether benzoin increases the solubility of the gases in the coating or increases the
diffusion constant of the gases through the coating or both has not been determined.
However, it is believed that, due to its volatility, benzoin increases the free volume in the
coating. As the benzoin leaves the coating, this free volume provides a path for the diffusion
of the trapped gases through the coating. Without the benefit of benzoin, the diffusion of the
gases through the coating is too slow, and the gases are trapped as the coating cures.