VOCs and HAPS for Air/Force
Paints
by Ron Joseph
ave Salman has been working at the EPA for
D as long as I can remember, and he and his for-
mer manager, Jim Berry, have been a fountain
of information, especially regarding EPA policies
that go back to the original Control Techniques
Guidelines (CTGs) of the late 1970s. In this month’s
column I have picked Dave’s brain by asking a broad
question for which I have never known the answer.
Dave is always most obliging and he gives lots of
thought to his answers. Thank you Dave! In presenting
his answer, I have made some minor editorial changes.
Many of the state regulations have a different VOC
limit for airlforce dry paints compared with those
that cure by oven baking. In states such as
California, the cut off is 194°F Typical VOC limits
are 3.5 lb lgal for airlforce dry coatings and 3.0
lb/gal for baked coatings.
I know of inspectors who will walk into a paint
facility and look at the oven temperature to deter-
mine if the coating inside should meet the airlforce
dry or the baking limit. An example of what can
happen is as follows: You apply an airlforce dry
coating but need to speed up the drying properties by
placing the coated part in an oven. The part is a
large casting that requires lots of heat to raise its
temperature to a modest 15O’F but to do this on lim-
ited factory floor space you raise the temperature in
the oven to 220°F An inspector who goes strictly by
the rule book finds that the oven temperature is
>194”F and issues an NOV because your coating is
at 3.5 lb lgal instead of 3.0 lb lgal.
What was the EPA rationale for setting the cut off at
194”FP Bear in mind that most coatings urulergo a chemi-
cal transformation (thermoset) at 250°F and, he- I don’t
understand how the 194°F value was arrived at.
There are two related questions. The older one
being “Is the bake temperature in the test high
enough to cause the curing reaction to take place so
that cure volatiles that are created during produc-
tion cure of the coating are generated and counted?’
The more recently raised question “Is the bake tem-
perature in the test high enough to cause the curing
reaction to take place so that reactive monomers can
react as they do in production cure of the coating
rather than evaporate as they would/might at a
Ron Joseph is an independent coating consultant in San Jose,
Calif. E-mail, drrojo@aol.com.
September 2002
Dry
temperature that is high enough to cause volatiliza-
tion, but not high enough to cause the curing reac-
tion to take place?”
This goes back at least to D 2369-73 (and maybe
even back to the original D 2369-65 of which I have
never seen a copy), which was intended for air-dry
solvent-borne coatings and specified 30 minutes
bake at 110°C (230°F).
When you first raised the question with me in a class
that you gave recently, I wrote: ‘The 1977 EPA CTGs
extended the application of the method to baking coat-
ings and led to a change in bake time from 30 minutes
to one hour.” There was some discussion about the
potential for adding higher bake temperature require-
ments in a memo describing a meeting that Jim Berry
went to in California. I think the meeting was at CARB
in April 1978 and was attended by several legendary
paint chemists such as Zeno Wicks from North Dakota
State University. I now need to amend this slightly
First, the 1977 Volume II CTG still stated that the
method was for coatings “which are air-dried or
forced-dried; it is not applicable to any coating sys-
tems which requires a special curing process such as
exposure to temperatures in excess of 110°C (230°F)
to promote thermal cross-linking or exposure to
ultraviolet light to promote cross-linking.” Method
24 was proposed in October 1979 and finalized in
approximately December 1980. I have not looked it
up, but I do not believe that the method 24 proposal
was restricted to air-dried or forced-air dried coat-
ings. The proposal was concurrent with a proposal in
the NSPS for auto and light-duty truck (OEM) coat-
ing, so a method that did not address baked coatings
would not have made sense.
ASTM D 2369 was revised in 1981. The 1981 version
gave a choice of 20 minutes (I mistakenly indicated
before that it was 30 minutes> or a l-hour bake time,
both at 110°C. Eventually, the 2Ominute bake option
was discarded from Dv2369. The expansion of the scope
of Dv2369 to include baked coatings occurred between
May 1977 and sometime in 1981. I do not recall exactly
how the change occurred. Jim Berry may remember
more of this. A round robin must have been done for the
1981 revision to see if the precision would be improved
with a switch from 20 minutes to a l-hour bake. I sus-
pect this round robin included baking coatings.
The April 1978 memo discusses a higher bake tem-
61
perature, 140 to 150°C for baked coatings, but I do
not recall much exploration of the effect of a higher
bake temperature. I do not know why this was never
adopted by EPA or ASTM.
One exception that I can think of is in Method D
6053 Standard Test Method for Determination of
Volatile Organic Compound (VOC) Content of
Electrical Insulating Varnishes. The origin of this
method was a meeting between representatives of the
National Electrical Manufacturers Association
(NEMA) and EPA. There was a concern that at 110°C
certain (I think they were referred to as “solventless”)
varnishes would not cure and a significant amount of
monomer would be volatilized and counted as VOC.
They had been looking at a higher bake temperature
and a larger specimen size (something on the order of
1 g or 3 g as opposed to 0.5 g in D 2369). EPA sug-
gested they pursue this with ASTM. We meant the
NEMA representatives to address their concerns
with the D-01 committee on Paint and Related
Coatings, Materials, and Applications. Since the
NEMA members were all in the D-09 committee on
Electrical and Electronic Insulating Materials the
method was developed and approved in D-09. No one
in D-01 knew about it until after it was approved.
This led to some interesting discussions about com-
mittee responsibilities and scope and communication
between committees. EPA wrote a letter to NEMA
approving the use of D 6053-96.
There is now D 6053-00, which allows for an even
larger specimen (I think up to 10 g) that has not
been approved by EPA.
How does a company take into consideration the
nonsmog-forming volatiles, such as water, amines,
ammonia, and other compounds, that are emitted
during the baking process?
I am going to interpret this question as: How does a com-
pany take cure volatiles into consideration in the determi-
nation of weight traction VOC content of a coating?
Assume that all of the cure volatiles are generated in
Method 24, ASTM D2369 by which the coating in subject
ed to 110°C (230°F) for one hour In this scenario there is no
way of determining which, if any, of the cure volatiles are
not VOC (e.g., cure water, cure amines, cure ammonia). In
this instance the company will be reporting a larger
percentage of VOC than actually leaves the coating.
At the January 2002 ASTM D-01 meeting, Steven
Brunner from Heresite Protective Coatings made a pres-

Precision Cleaning Solvent

Effective and Environmentally Friendly
DS-Series Solvents
l leave No Residue . low Vapor Pressure
- Flashpoint Above lOOoF - Acceptable Odor
- low Toxicity . High Cleaning
- Non-corrosive Effectiveness
- Cost Effective - Meet Environmental
- EPA SNAP listed Regulations

Dynamold /‘-h
DSI Solvents, Inc.
290 1 Shamrock Avenue
(, q J

Fort Worth, Texas 76 107

(8 17) 3350862 Fax (8 17) 877-5203
www.dynamold.com
Before

-Inquire about FREE Brochure or Sample!

Circle 023 on reader card or go to www.thru.to/webconnect Circle 003 on reader card or go to www.thru.to/webconnect
62 Metal Finishing
entation that included a suggested methodology and pre
hminary results for determining cure water horn epoxy-
phenolic coatings. Some of his test results indicated as
much as 10% of the initial coating weight that is emitted is
lost as water as a result of the baking process.
If some of the volatiles that are only emitted above 250°F
are HAPS, how does the company account for them?
I am going to interpret this question as: If some of
the cure volatiles are HAPS (or if a coating generates
cure HAP), how does the company account for them?
Right now cure HAPS pretty much get a free ride.
This applies to cure HAPS that form below 250°F and
those that form only above 250°F. This is why I left
the temperature out of my rewording of the question.
The EPA method for HAP content of coatings is
Method 311. This is a direct-injection gas chro-
matograph (GC) method, which we believe will
detect and count HAP present in the as-sold/pur-
chased (wet) coating, but will not generate and,
therefore, will not detect and will not count cure
HAP. If “formulation” data are used in place of
Method 311 data, then cure HAP will most likely
not be counted because the formulation data will
identify and quantify only those HAPS that are
present in the as sold/purchased coating. The start-
ing point for this is usually data from the raw
material supplier, which identifies HAPS present
at 1.0% by weight or greater (0.1% or greater for
carcinogens) in the raw material.
We have had lots of discussion about this during
development of the MACT rules, particularly in
regard to cure formaldehyde. Some work was done in
our emission measurement center on developing a
cure formaldehyde measurement procedure to append
to Method 311. The ASTM D-01 group has also been
working on a method for cure formaldehyde. This
work has been led by John Phillips at Ford.
So far, I do not think any of the MACT rules explic-
itly require cure HAP to be counted. Another option
in some of the MACT rules is to use weight fraction
organic volatile content (as determined by EPA
Method 24, ASTM D 2369) as a surrogate for weight
fraction organic HAP content. If someone does this
and the EPA Method 24, ASTM D 2369 test gener-
ates cure volatiles then this would be counted in the
weight fraction of the VOC content.
A flip side to this question is how do you count (or
not count) HAPS that are reactants present in the as
sold/purchased coating. For example, in printing
there are some reactive adhesives with high levels of
TDI or MD1 included as a reactant. Method 311
would count these HAPS since they are present in
(one component of) the as sold/purchased coating. In
practice, I suspect that users are largely discounting
September 2002
the reactant HAP. (One way to handle this analyti-
cally might be to establish weight fraction organic
volatile content using EPA Method 24, ASTM D 2369
and use that value as an upper bound for HAP con-
tent. For example, if a material has 40% by weight
styrene monomer then Method 311 will count this as
40% by weight HAP, but if only 10% by weight of the
material volatilizes when tested by D 2369 then it is
not emitting more than 10% by weight HAP. Both of
these allow for an induction time when testing mul-
ticomponent coatings to allow for the reaction to take
place. Most of the MACT rules do not explicitly
address this, although I think at least one of the
rules still in development does say something about
this; but I do not remember which rule it is. There
may be some ongoing discussion about reactive adhe-
sives in the plastic parts coating MACT.
BIOGRAPHY
Dave Salman is an Environmental Engineer in the
Coatings and Consumer Products Group, Emission
Standards Division, Office of Air Quality Planning
and Standards, Office of Air and Radiation of US EPA.
MF
FREE SAMPLES U FREE GIFT
ToPROVE YOU’LL SAVE $$, CLEAN BETTER AND
COMPLY WITH EPA, OSHA AND CALIFORNIA
GREEN POWER
PQUEOUS PARTS WASHING DEGREASER
THE METAL WORKER’S CHOICE
Ieans and strips away wax, flux, coolants, oil, paints, optics, etc. Designed to help
separate oils and grease with oil skimmers. Minimizes toxic waste removal. SAFE
or ALL brands of aqueous pans washers, deburring, ultrasonics, floor scrubbers,
lressure and steam cleaners. Phosphate free and rust inhibited. CAUTION:
drmakleen, Oakite, Planisol, TASC or ZEP users, you may have to use less “Green
‘owe?.
FHE NATURAL
ADHESIVE AND RESIN STRIPPER
THE ENVIRONMENT’S CHOICE
qeplaces acetone, MEK, 1 ,l ,l, trichloroethane and other flammable hazardous
solvents. Strips away and dissolves urethane, epoxy, cyanoacrylate, polymer
and other adhesives and resins, paints, etc. Safe for the environment.
RAPID RINSE
ENVIRONMENT FRIENDLY SOLVENT
THE SLA MANAGERS CHOICE
Stereolithography rinse agent. Removes CBA-GEIGY, ALLIED SIGNAL, 3D
SYSTEMS and other rapid prototype resins. Other uses: dissolves grease, oil,
oaint adhesives and resins. Replaces flammable and hazardous solvents.
TIRED OF ALL THE PROMISES FROM SAFETY COMPANIES
THAT HAUL AWAY TOXIC WASTE AND LEAVE YOU
HOLDING THE LlAGlL17-Y BAG7
GO WITH =GREEN POWER” EARTH FRIENDLY PRODUCT
LINE OF PROVEN ALTERNATIVES
GREEN POWER CHEMICAL
Call: 800-932-9371 USA * CANADA * MEXICO
Fax: 973-691-1058 International: 973-691-5474
60 River Road Stanhope, NJ U.S.A. 07874
l
www.greenpowerchemical.com
Circle 035 on reader card or go to www.thru.to/webconnect
63