Part 9: Films for Testing
MNL17-EB/Jun. 1995
Cure: The Process and Its
Measurement
by Thomas J. Miranda 1
INTRODUC~ON
One of the most critical, and often misunderstood proper-
ties of a coating is cure and its measurement. The optimum
physical and chemical properties of a coating depend largely
on proper curing conditions. For example, a thermosetting
acrylic polymer when applied to a panel and dried without
curing will be brittle and have poor solvent resistance and low
hardness. When properly cured, the film properties will
change dramatically and the properties which were designed
into the coating become apparent. Similarly, an oil-based
paint will be soft and tacky and slowly become hard and
scratch resistant as its cure develops. To appreciate the scope
of the material in this chapter, it may be well to review a few
film-forming mechanisms, polymer fundamentals, and some
background into the development of tests and what they
mean.
Background and Film Formation
Polymers
A polymer is a high-molecular-weight interreaction prod-
uct of related polyfunctional molecules [1 ]. The term polymer
is derived from the Greek poly (many) and met (part). Poly-
mers are formed from monomers (mono -- one) (met -- part)
by a process of polymerization. Polymers consist of long
chains of macromolecules with molecular weights of a few
thousand up to many millions. For example, ultrahigh-mo-
lecular-weight polyethylene may have a molecular weight of 4
to 6 million, while alkyds have molecular weights of a few
thousand. The concept of macromolecules was developed by
Herman Staudinger in 1920 [2]. Staudinger's theory was
supported by the work of Wallace Carothers, who introduced
the concept of functionality and the distinction between ther-
moplastic and thermosetting polymers [3].
There are two types of polymers: addition and condensa-
tion. Addition polymers have high molecular weight and are
characterized by fast chain reaction syntheses that are exo-
thermic and initiated by free radical, coordination polymer-
ization, cationic, group transfer, or anionic mechanisms.
Free radical-initiated polymerization is initiated by incorpo-
ration of a free radical producer such as benzoyl peroxide
which decomposes with heat to form free radicals, which in
turn initiate polymerization. Coordination polymerization is
Senior Consultant, Consolidated Research, Inc., 16731 Brick Rd.,
Granger, IN 46530.
407
Copyright9 1995 by ASTMInternational www.astm.org
i
36
initiated by complex initiator systems such as those used to
polymerize ethylene or propylene and sometimes referred to
as Ziegler-Natta catalysts made from an organometal and an
inorganic compound like titanium tetrachloride. Cationic ini-
tiation can be done using Lewis acids such as aluminum
chloride or boron trifluoride and are usually carried out at
low temperatures. Butyl rubber is made by such a process.
Group transfer is a relatively new type of polymer initiation,
while the anionic processes use organometals (butyl lithium)
to produce polymers. Block polymers are made by anionic
processes. Condensation polymers have lower molecular
weight than addition types and are produced by stepwise
addition with elimination of water as a byproduct and require
a longer time to synthesize using an endothermic process [4].
Cure Concept and Illustrations
We can simplistically illustrate the concept by considering
a long chain polymer (thermoplastic) as a wire fence with a
number of strands (Fig. I) such as used on a farm. An individ-
ual can pass through the fence by spreading the strands apart,
and standing on the fence will cause the strand to sag or
elongate. If, however, we take that fence and lace it with wire
such that a hogwire fence is produced, then we see the
changes in the physical properties of this (thermoset) fence.
First, it would be difficult to pass through the fence; second,
one can stand on the fence since it is stronger and will not
yield as would the single strand fence. If one considers the
ability to pass through the fence as solvent action, it is easy to
visualize how solvent molecules can permeate and dissolve a
thermoplastic polymer, but difficult or impossible to dissolve
a thermoset polymer. In fact, a thermoset polymer will tend
to swell, such as a rubber band in a hydrocarbon solvent. This
is because the solvent molecules can solvate the linear por-
tions of the rubber, but are constrained by the sulfur cross-
links from totally dissolving the polymer. Another aspect of
cross-linking is that the molecular weight increases enor-
mously, which explains why solvent resistance increases and
certain physical properties such as hardness, scratch resist-
ance, and toughness are enhanced. The thermoset polymer is
a three-dimensional network polymer. Cure must not be con-
fused with dry time such as that measured in oil-containing
polymers which dry by interaction with atmospheric oxygen.
Here such terms as set-to-touch, print free, time to lint free, and
time for sand pickup relate to the speed at which solvent
evaporates and not to the ultimate cure or cross-linking of a
coating system. Cure, therefore, refers to the cross-linking of
a polymer to produce a three-dimensional network.
408 PAINT AND COATING TESTING MANUAL

THERMOPLASTIC (no c r o s s l i n k i n g ) CURE MECHANISMS

S S S
S S
S S
Coating films can be made by a number of methods. The
principal mechanisms of film formation are represented by
S lacquers, emulsions, and thermosetting (via oxidative cross-
linking or by reactive cross-linking) coatings. For a review of
film formation, the reader is referred to the Federation of
Societies for Coatings Technology Monograph on Film For-
mation [5].

THERMOSET (crosslinking) Lacquers

s s s Lacquers consist of a thermoplastic polymer which is dis-
solved in a solvent. When the coating is applied, the solvent
I I evaporates and a thermoplastic film is formed. This is the
type of coating used in certain furniture and automotive

S
I S
l S
finishes.

S = solvent molecules Emulsions

= linear polymer
[ = crosslinked segments
FIG. I-Polymers.
TYPES OF FILMS
As described above, polymers can be classified as thermo-
plastic and thermoset in nature when derived from addition
and condensation polymerization as well as by their physical
response to heat and solvent action.
Thermoplastic
A long-chain polymer such as polyethylene is considered
thermoplastic since it can be dissolved in certain solvents and
can be repeatedly softened or melted when heated and hard-
ened when cooled.
Thermoset
On the other hand, a polymer prepared, for example, from
a phenol-formaldehyde condensate cannot be liquified and
solidified repeatedly after it is formed. These polymers are
termed thermosetting and tend to degrade if heated repeat-
edly. The reason for this is that they are cross-linked.
Another means for forming a thermoplastic film is film
formation from an emulsion. In this case, a polymer, such as
a vinyl acetate-acrylic copolymer emulsion (or latex), is cast
onto a substrate and then the water carrier leaves the film by
evaporation. In the latex, water is not a solvent but a dispers-
ing medium. Microscopically, the polymer molecules look
like tiny ball bearings suspended in water (Fig. 2). Surface
active agents keep the polymer from settling. As the water
evaporates, hydrodynamic pressure causes the small spheres
to crowd closer and closer together until capillary action
forces the particles to fuse and form a continuous film. If the
polymer is too hard, a poorly adherent film forms. This is why
paint manufacturers recommend that water-based, latex-
type paints not be applied at low temperatures. At low tem-
peratures, the particles cannot fuse properly, and the paint
will fail prematurely. To facilitate fusion, small amounts of
coalescing solvent such as diethylene glycol monobutyl ether
(butyl Carbitol TM Union Carbide Corp.) are added. These sol-
vents lower the glass transition temperature of the copolymer
and facilitates fusion. These are examples of physical drying
as compared to chemical drying discussed next (see Fig. 2).
Oxidative Cross-Linking
In oxidative cross-linking, a polymer is prepared from an
unsaturated fatty acid or oil such as castor, tall, soya, linseed,
or tung oil, and a small amount of a siccative (drier) such as

OWOWOWOWOWOWOWOWOWOWOW Latex on surface

W W W W W W W W

0000000000OO000000OOOO Water evaporates

Fused film

O=Polymer particles

W=Water
FIG. 2-Drying of a latex film.
 CHAPTER 36--CURE: THE PROCESS AND ITS M E A S U R E M E N T 409

lead, cobalt, manganese, or zirconium salts, for example, Melamine can be condensed with up to 6 mol of formalde-
naphthenates, octoates, etc., is added. The film is cast by hyde and 6 mol of methanol to form hexamethoxymethyl
brushing, spraying, or other means and allowed to dry. In the melamine (HMMM). The reaction product has the following
first stages, the solvent evaporates, leaving a tacky film. The structure and is often referred to as MF resin:
film can be easily deformed or thumb printed. But, as the film
ages, it slowly becomes less tacky and finally print free and N(CH2OCH3)2
cured. What has happened? The film slowly absorbed oxygen
from the atmosphere and formed hydroperoxides on the car- /A
bon alpha to the double bond. The drier decomposed the N N
hydroperoxide and formed free radicals that initiated cross- t II
(CH3OCH2)2N--C C--N(CH2OCH3)2
links between the chains derived from the fatty acid portion
of the alkyd (which imparts improved properties to the film), N
resulting in a cured or cross-linked film. A simplified reaction Hexamethoxymethyl melamine
scheme is shown in the following [6]:
Hexamethoxymethyl melamine can be reacted to contain
R--CH=CH--CH2--CH~-~-CH--R' 02 )
from one to six methoxymethyl groups. Methanol is used to
R--CH--CH=CH--CH~-~CH--R' cap the hydroxyl group to prevent premature reaction. Other
I alcohols are commonly used, including butanol and isobu-
OOH tanol. In applying a melamine formaldehyde resin, the resin
R--CH--CH=CH--CH~---CH--R' + .OOH usually is reacted with a functional polymer such as a ther-
mosetting acrylic or alkyd polymer containing an acid or
where R is CH3(CH2) 4 and R' is (CH2)TCO2CH 3. hydroxyl group that can react with the MF resin. This can be
depicted in the following manner:
The initial products are converted to polymers according to:
Initiation: RH + 02 ) R" + "OOH 2 Polymer--[- + M--N(CH2OCH3)2 )
1

CH2OH
Propagation R" + 0 2 ) RO0"
Polymer-----[--
RO0" + RH ) ROOH + R"
CH2(~
Termination RO0" + R" ) ROOR
RO0" + ROO" > ROOR + 02 / CH2
M--N + 2CH3OH
R'+R" >R--R \
CH~
Termination by coupling doubles the size of the molecule I
since two fragments are now joined (assuming that the chain CH20
length is about equal). In this way oil-bearing oxidative Polymer I
curing leads to networks having the proper chemical and
physical properties. where M denotes a methoxy-substituted melamine functional
unit. In this illustration, only two of the melamine meth-
oxymethyl functions are shown reacting with the hydroxyl
Reactive Cross-linking groups of an alkyd or other hydroxyl functional polymer.
In this type of cross-linking, a reactive intermediate is Note also the formation of a byproduct, methanol. Formalde-
added to a polymer and a further chemical reaction is initi- hyde can also form as a byproduct.
ated either by heating alone, heating in the presence of a
catalyst, or by some other form of initiation.
Urea
Melamine A scheme similar to that described above for melamine is
Melamine formaldehyde condensates are used to cure also applicable to urea formaldehyde (UF) resins. In this case,
a reactive polymer. Melamine is 1,3,5 triamino-s-triazine urea is reacted with formaldehyde and endcapped with either
and is produced from the condensation of 3 moles of methyl, butyl, or isopropyl alcohols. A fully reacted urea in-
dicyandiamide: termediate would have a structure
NH2
(CHaOCH2)2--N--C --N--(CH2OCH3) 2
II
0
I iL N,N' bishydroxymethylurea
H2N--C C--NH 2
and is capable of reacting with hydroxyl groups to produce a
N
cross-link with the elimination of byproducts as water, alco-
Melamine hol, and formaldehyde.
410 PAINT AND COATING TESTING MANUAL

Epoxy ings, and high-performance coatings such as for aircraft. In

Epoxy resins are derivatives of cyclic ethers. Aromatic ep- this case the isocyanate is a di- or triisocyanate, which leads
oxy resins are produced from the reaction of epichlorohydrin to cross-linking. Toluene diisocyanate is widely used, hut
and bisphenol A, and the latter is a condensation product of other isocyanates such as 1,4-diphenyl methane diisocyanate,
acetone and phenol. Aliphatic epoxy resins are prepared by isophorone diisocyanate, and trimers of hexamethylene di-
the peroxidation of unsaturated linear or cyclic olefins. A isocyanate are also used. The higher-molecular-weight isocy-
simple epoxy, the diglycidyl ether of bisphenol A, is shown anates are preferred for their lower vapor pressure, thus pro-
below (Z = phenylene group) viding for improved working conditions.
Isocyanates are used to cross-link a variety of polymers
O CH3 O containing hydroxyl or amine functionality. In the case of
/\ i
CH2--CHz--O--Z--C--Z--O--CHz--CH--CH2
/\ amine functionality, a urea cross-link is formed. For example,
an acrylic polymer can be prepared from methytmetha-
[ crylate, butyl acrylate, and hydroxyethyl methacrylate. This
CH3 polymer can be cross-linked through the pendant hydroxyl
These epoxy functional groups can react with active hydro- groups of the hydroxyethyl methacrylate portion by poly-
gen groups such as amines, hydroxyls, and acids. For exam- functional isocyanates:
ple, they can react with acid groups in a thermosetting
Acrylic polymer
acrylic, alkyd, or other polymer and produce a cross-linked I
polymer. It is interesting to note that the reaction product of (CH2)2
the epoxy and acid function produce additional hydroxyl I
O--C~-~O
groups which can be reacted with a melamine formaldehyde
or urea formaldehyde adduct to produce improved proper- t
HN T NH
ties, such as hardness, chemical resistance, or solvent resist- I
ance in the cured films. The reaction of two acrylic polymer O=C--O
chains with an epoxy resin is shown as follows: I
(CH2)2
[ Acrylic polymer
Acrylic polymer
COOH
0 0 Urethane cross-linked acrylic
CH3
/\ i /\
CH2--CH--CH2--O--Z--C--Z--O--CH2--CH--CH2Epoxy resin
T = CH3--C6H 3- (from toluene diisocyanate)
I Urethane cross-linking is also used in polyesters where the
CH3 hydroxyl groups are obtained from polyfunctional alcohols,
COOH such as trimethylolpropane or pentaerythritol. Similarly, ep-
I Acrylic polymer oxy resins can be cross-linked through the hydroxyl groups
formed during epoxy reactions.
l
I
Acrylic polymer Catalyzed Cross-linking
C=O This type of cross-linking is used in phenolic and silicone
I H
O reactions wherein a catalyst is added to facilitate the cross-
O CH3
I I I linking reaction.
CH~ CH--CH2--O--Z--C--Z--O--CH2--CH CH2
Phenolics
t
CH3 OH O Phenolic resins are condensation reaction products of phe-
I nol or substituted phenols and formaldehyde. Two types of
C-~O
I phenolics are obtained depending upon the catalyst and reac-
Acrylic polymer tion conditions. Using an acid in its preparation, a thermo-
where Z represents a phenylene group. plastic, soluble novolac resin is obtained. Under basic condi-
tions, the thermoset product formed is a resole resin which is
Cross-linked acrylic polymer cross-linked at the final stages of the reaction. A phenol-
Isocyanates formaldehyde condensate may have a structure as shown:
The term urethane applies to the reaction product of an OH
hydroxyl group and an isocyanate. For example, an alcohol I
and isocyanate react by rearrangement to produce a urethane
C C
CH3--CH2--OH + R - - N ~ C = O ~R--N--CqO If I
L I HOH2C--C C--CH2OH
H O--CHz--CH3 \//
Alcohol + Isocyanate Urethane C

This reaction is used in applying isocyanates to the produc- CH2OH

tion of insulation and seating foams, reaction injection mold- Phenol-formaldehyde (P--F) condensate
 CHAPTER 36--CURE: THE PROCESS AND ITS M E A S U R E M E N T 411

Alkyd resins can be cross-linked by reaction of the hydroxy- source for initiation. Electron beam (EB) and ultraviolet radi-
methyl function and an hydroxyl group on the alkyd with the ation is used to cure coating films. These processes induce
elimination of water: either free radical or carbonium ions to initiate polymeriza-
tion, which occurs rapidly at ambient conditions.
OH
I
/C\~ HEAT CURE MEASUREMENT
2 + HOH2C--C C--CH2OH
I II I
CH2OH C C It is very important for the user of coatings to know
\// whether a coating is adequately cured. This can be done
C quickly in qualitative testing or in more sophisticated test
methods requiring instrumentation. The rapid methods are
CH2OH
desirable because of time and cost, but in some cases do not
Alk, 'd Phenol-Formaldehyde Condensate really tell the true story. In some cases, even instrumented
f testing only tests a certain range of cross-linking and could
lead to erroneous conclusions. We shall discuss the qualita-
--CH20 H2C--C C--CH2 OH2C-- + 2 H20 tive methods first, then proceed to the more quantitative.
II I What should be borne in mind is that we are attempting to
C C ascertain a molecular process, cross-linking, and its relation-
\//
C ship to coating performance.
I Many thermoplastic coatings "dry" by simple evaporation
ALKYD CH2OH ALKYD of solvent, and though cure was defined above as the cross-
Cross-linked alkyd linking of a polymeric system, such drying of lacquers can be
considered a form of curing even though no cross-linking
Silicones occurs. This is true for nitrocellulose lacquers, cellulose ace-
These useful polymers are prepared from silicon by chlo- tate, and solvent soluble acrylics where no cross-linking takes
rination, then subsequent reaction with alkyl or aryl halides place. To measure cure for such coating, the time for either
to form alkyl/aryl chlorosilanes. Upon hydrolysis, these pro- print-free or tack-free is measured. At some time during evap-
duce silicones. The alkyl silicones, such as dimethyl silicone, oration, the coating goes from tacky, to set-to-touch, to tack-
free. Upon further drying, the coating becomes print-free,
CH3 whereby a thumb print will not be visible on the coating. This
I
[ Si O--]n-- can also be measured by dropping cotton linters onto the
J surface and noting the time after which they do not adhere to
CH3 the coating. Also see ASTM D 2091, which describes a stan-
dard method for print resistance of lacquers.
are low-molecular-weight or cyclic materials used in anti-
These tests also apply to coatings which dry by oxidative
foam applications. The linear forms are specialty elastomers.
cross-linking, for example, alkyds. Here, times are noted for
Blends of methyl and phenyl silicones have higher-tempera-
ture resistance and find use in heat-resistant coatings or poly- solvent evaporation, and the coating is monitored for set-to-
mers. Silicones can be cross-linked when prepared with mul- touch, then print-free.
ti functional silane monomers such as trichloromethyl silane.
Upon hydrolysis, the silicone chains can be cross-linked Solvent Rubs (ASTM D 4752 Test Method for
through siloxane bridges: Measuring MEK Resistance of Ethyl Silicate
(Inorganic) Zinc-Rich Primers by Solvent Rub)
CH3
f A convenient, often-used method for determining cross-
[ Si O--].-- linking involves solvent rubs. A cloth soaked with methyl
I ethyl ketone (MEK) is rubbed vigorously on the film, and then
O
the film is examined after a specific number of rubs. Acetone
I
[ Si O--In- is also used for this test. If the film is removed, softened, or
[ loses gloss, then the film is considered not adequately cross-
CH3 linked. Films which are unaffected are considered cured. For
Cross-linked silicone example, certain acrylic, epoxy, or polyester coatings can
survive this test. The problem with this test is that the individ-
Silicones can also be cross-linked by peroxide initiators. In ual testing the coating is not standardized. One person may
this case a silicone monomer containing a vinyl or allyl group exert much more pressure than another, and this can affect
is copolymerized to provide an active site along the chain. the final result.
When used in a gasket or caulk, a small amount of a peroxide
is added which initiates polymerization and cross-links the
Hardness Measurements
resin system. Silicone reactions are usually catalyzed by 01"-
gano zinc or tin compounds. Another way of obtaining information concerning cross-
Curing can also be accomplished using radiation as a linking is to measure some physical property such as, hard-
412 PAINT AND COATING TESTING MANUAL
ness, scratch resistance, or impact resistance. There are a
number of tests which provide this information.
Knoop and Pfund Hardness (ASTM D 1474 Test
Methods for Indentation Hardness or Organic
Coatings)
A useful test of cure is to measure the Knoop hardness in
which a pyramidal diamond indenter is pressed into the film
to cause indentation. The method is described in ASTM
D 1474. A weight is applied to the indenter for a specific time,
and the length of the indentation line is measured with a
microscope. The Knoop hardness number (KHN) is calcu-
lated from [8]:
KHN = L/Ap = L/lZCp
where L = applied load (kg), Ap = projected indentation area
(mm2), l = length in mm of the long diagonal of the indenta-
tion mark, and Cp is an instrument constant. Because of the
thinness of coating films, this method is more useful in plas-
tics since it requires almost a 75% indentation into the film
and can be influenced by substrate considerations.
The Pfund Hardness Number (PHN) is obtained using a
hemispherical quartz or sapphire indenter, which is pressed
into the film. The Pfund Hardness Number is calculated
from:
PFN = L/A = 4L/wd2 = 1.27 L/d 2
where
L = applied load in kilograms,
A = area of projected indentation in mm 2, and
d = diameter of the projected indentation in mm.
Sward (See ASTM D 2134, Sward Rocker, and ASTM
D 4366, Pendulum Damping)
Sward hardness depends upon the change in surface prop-
erties and viscoelastic properties of a film. This method,
which was discontinued in 1990, is used for automotive fin-
ishes and consists of a rocker containing two spirit bubble
indicators. The pendulum is rocked, and the number of
swings are recorded and a reading taken at the point where
the swings are equal to half the original value. Several types
of pendulum units are used including Sward, Perzoz, and
Koenig. As cure increases, the Sward number increases. The
value of a Sward test is that a n u m b e r is obtained which can
be compared to other coatings. This test must also be con-
ducted under very clean conditions, as lint and surface imper-
fections can interfere. Temperature control is important in
this test as in other tests involving determining physical prop-
erties of coatings. The problem with this test is that it only
measures cross-linking density to a point; then cannot detect
over cure since a plot of Sward numbers versus cure tends to
reach a limiting value. A comparison of values obtained by
different test methods is shown in Table 1 [9]. Note how the
values differ, especially between different brands of pencils
and the limiting value of Sward Hardness.
Pencil (ASTM D 3363 Test Method for Film Hardness
by Pencil Test)
Pencil hardness is a test which was developed by the manu-
facturers of pencils who tried to develop a means for checking
the quality of pencils. Someone suggested scratching a paint
film, and it was noticed that the different hardnesses of pen-
cils were able to penetrate through the coating. This test was
later used by coating technologists, and it is widely used in
the industry today. In this technique a number of pencils with
known hardnesses are employed. The pencil is t r i m m e d so
that 5 mm of lead is exposed. The lead diameter is 1.8 m m
and is sharpened by rubbing it perpendicular to the surface of
No. 400 carbide abrasive paper. The pencil is held at a 45 ~
angle to the coating and pushed along the surface to peel
away the coating. The pencil which fails to scratch the coat-
ing is the value used as pencil hardness. This method is
simple, the equipment low in cost, and the results can be
quickly obtained. However, values can differ depending upon
the operator, the method of sharpening the lead, and the
variances of lead hardness from different pencil lots and
manufacturers.
Gardner Impact (ASTM D 2794 Test Method for
Resistance of Organic Coatings to the Effects o f Rapid
Deformation (Impact))
This is a valuable test which measures the impact resist-
ance of a coating and can be used to correlate with cure. An
undercured coating may exhibit a lower Gardner Impact
value, but as cross-linking density increases, the impact val-
ues improve. The test consists of placing a coated flat panel
under a weighted spherical ball assembly and then dropping
the weighted ball onto the panel from different heights. The
cylinder in which the ball assembly is mounted is calibrated
such that an operator can measure the impact directly in inch
pounds. Impact measurements are done by dropping the ball
directly on the coating surface or on the reverse side. The
results are reported as inch-pounds direct or reverse. Direct
impact is less severe than reverse impact. A dimple is formed
in the test panel which can be examined visually or with a
X10 glass to determine the extent of cracking which occurs.
An appliance acrylic may have a direct impact of only 10
in.-lb, while a polyester urethane powder coating may have a
reverse impact of 160 in.-lb. The value of the Gardner Impact
test is that the test can be done quickly, it is widely recognized
in the coatings industry, and it gives some correlation with
cross-link density in that the optimum physical properties of
a coating develop as the molecular weight increases.
Thermal Analysis
Thermal analysis is an important analytical tool for deter-
mining the response of material to changes in temperatures.
This method of analysis can be used to monitor the glass
transition temperature, Tg, of a coating, and this can be re-
lated to the cross-linking density. For example, a ladder of
paint panels cured at various times or temperatures can be
prepared and then studied by thermal analysis to determine
the change in Tg as a function of bake schedule. From this, the
optimum cure cycle can be determined to insure a quality
finish.
Thermal analysis units have several modes for determining
Te: differential scanning calorimetry (DSC), thermo-
mechanical analysis (TMA), and dynamic mechanical analy-
sis (DMA) are useful tools for obtaining quantitative mea-
 CHAPTER 36--CURE: THE PROCESS AND ITS MEASUREMENT 413

TABLE l mHardness test correlation.

Pencil (Brands)
Panel No. KIlN Sward A B C D E
1 3.09 24 5B 6B 5B 6B 4B
2 4.33 28 4B 6B 6B 6B 4B
3 2.77 24 5B 6B 5B 4B 3B
4 2.61 22 3B 4B 5B 4B 3B
5 5.81 38 2B 2B 2B 2B HB

10 25.7 54 H H H H 2H

12 39.1 40 3H 2H 2H 4H 3H

14 40 8H 9H 7H 7H 9H

sures of cross-linking b y m e a s u r i n g Tg. The glass t r a n s i t i o n Impedance Measurements

t e m p e r a t u r e is a s e c o n d o r d e r t r a n s i t i o n t h a t r e p r e s e n t s a
t e m p e r a t u r e w h e r e segmental m o t i o n occurs along a p o l y m e r
c h a i n backbone, a n d it is a c c o m p a n i e d by a volume change. A
c o m p a r a t i v e s t u d y of changes of cross-linking m e a s u r e d b y
S w a r d hardness, evaporative rate analysis, a n d DSC s h o w e d
t h a t Tgchanges c a n be followed to high levels of cross-linking,
w h e r e a s S w a r d m e a s u r e m e n t s r e a c h e d a limiting value while
Tg c o n t i n u e d to rise [10].
W i t h DSC, a plot of e n d o t h e r m / e x o t h e r m is m a d e as a
function of t e m p e r a t u r e at a set rate of t e m p e r a t u r e rise. As
the Tg is reached, there is an a b r u p t change in the e n d o t h e r m
w h i c h a p p e a r s on a plot. Similarly, Tg can be m e a s u r e d using
a plot of c h a n g e in e x p a n s i o n with t e m p e r a t u r e with the TMA
mode. Here a s a m p l e is p l a c e d u n d e r a quartz p r o b e a n d t h e n
heated. As the film expands a plot is o b t a i n e d in w h i c h a
change in slope occurs. The intersection of the tangents of the
e x p a n s i o n curve yields the Tgvalue. I n the p e n e t r a t i o n m o d e a
d e p r e s s i o n occurs indicating the Tg. Plots can be m a d e of Tg
versus b a k e cycle to note the o p t i m u m Tgof a coating. F u r t h e r
details on t h e r m a l analysis a p p l i c a t i o n s can be f o u n d in the
literature [11 - 13 ].
Dynamic Mechanical Analysis
Another w a y of o b t a i n i n g Tg is to use d y n a m i c m e c h a n i c a l
analysis in which a coating film is fixed to the ends of a tuning
fork a n d the fork driven over a frequency range a n d at differ-
ent t e m p e r a t u r e s o r at a fixed frequency w i t h varying t e m p e r -
ature to provide a plot of d a m p i n g versus t e m p e r a t u r e . This
i n f o r m a t i o n yields Tg as well as m e c h a n i c a l d a m p i n g infor-
m a t i o n a b o u t the film [14].
Torsion Pendulum [14,15]
A n o t h e r m e t h o d for m e a s u r i n g d y n a m i c m e c h a n i c a l p r o p -
erties of coatings is to s u s p e n d the film with a weight, then
twist the weight so that it will oscillate as a p e n d u l u m . This is
not entirely acceptable since coating films m a y n o t have the
strength to s u p p o r t the weight of the a p p a r a t u s . One way to
o v e r c o m e this is to invert the a p p a r a t u s so that the p e n d u l u m
weight is s u s p e n d e d w i t h counterweights. A m o r e practical
m e t h o d is to use the t o r s i o n b r a i d p e n d u l u m in w h i c h a
fiberglass b r a i d is s a t u r a t e d w i t h a coating a n d the p e n d u l u m
oscillated. As the coating cures, changes in oscillation can be
c o r r e l a t e d with d a m p i n g a n d Tg.
Myers [16] s t u d i e d the drying behavior of latex systems
using ultrasonic i m p e d a n c e m e a s u r e m e n t s , I n this work, a
latex coating was cast on a quartz crystal a n d ultrasonic en-
ergy was b e a m e d at an 11 ~ angle at the u n d e r s i d e of the
coating a n d reflected to a d e t e c t o r w h i c h m e a s u r e d the atten-
u a t i o n of the initial b e a m as a b s o r b e d by the drying coatings.
As w a t e r evaporated, there were changes in i m p e d a n c e t h a t
could be c o r r e l a t e d to drying.
Evaporative Rate Analysis
A novel m e t h o d for studying cure is evaporative rate analy-
sis (ERA) developed by John Anderson [17]. This w o r k was
carried out to d e t e r m i n e the cleanliness of the surface of
spacecraft. Anderson r e a s o n e d that if a radioactive C 14 liquid
w o u l d be p l a c e d on a clean surface, the e v a p o r a t i o n rate
would be r e t a r d e d due to cleanliness. In fact, however, the
opposite was true.
Nevertheless, this m e t h o d was developed to m e a s u r e de-
gree of cleanliness. If a small a m o u n t of diethyl succinate-C -14
is d e p o s i t e d on a surface a n d a controlled sweep of n i t r o g e n is
applied, the rate of e v a p o r a t i o n can be m o n i t o r e d using a
Geiger counter. The principle is that on a clean surface there
is no i n t e r a c t i o n between the solvent a n d the clean substrate,
a n d n o r m a l e v a p o r a t i o n occurs. If, however, the surface con-
tains a c o n t a m i n a n t , then the radioactive liquid will interact
with the surface c o n t a m i n a n t a n d r e t a r d the rate of evapora-
tion of the r a d i o c a r b o n . Plots c a n be o b t a i n e d relating clean-
liness to e v a p o r a t i o n rate.
Anderson a p p l i e d this technique to the cure of organic
coatings. H e s h o w e d t h a t in an u n d e r c u r e d surface solvent
r e t e n t i o n increased, leading to longer residence of the ra-
d i o c a r b o n on an u n d e r c u r e d surface. This is u n d e r s t a n d a b l e
in view of the example given in the beginning of this c h a p t e r
of the ability of a solvent to pass t h r o u g h a wire fence anal-
ogy. By p r e p a r i n g c o a t e d panels having different cure times
o r t e m p e r a t u r e s , t h e n m e a s u r i n g the ERA of each panel, a
plot of r e t e n t i o n versus bake is obtained. This m e t h o d was
a p p l i e d to the m e a s u r e m e n t of cure of a variety of coatings by
m a n y coatings technologists [10,18]. The only p r o b l e m was
t h a t there was no quantitative m e a n s for m e a s u r i n g the rela-
tionship of ERA to cure until it was s h o w n that DSC of Tg
414 PAINT AND COATING TESTING MANUAL
could be correlated to the values obtained using ERA mea-
s u r e m e n t s [10].
REFERENCES
[1] D'Alelio, G. F., Fundamental Principles of Polymerization, John
Wiley & Sons, Inc., New York, 1952, pp. 5-22.
[2] Staudinger, H., Uber Polymerization, Vol. 53, 1920, pp. 1073-
1085.
[3] Mark, H. and Whitby, G. S., Eds., Collected Papers of Wallace
Hume Carothers on High Polymeric Substances, Interscience,
New York, 1940.
[4] Paul, S., Surface Coatings, Chapter 1, John Wiley & Sons, New
York, 1985.
[5] Wicks, Z. W., Jr., Film Formation, Federation Series on Coatings
Technology, Blue Bell, PA, June 1986.
[6] Paul, S., Surface Coatings, John Wiley & Sons, New York, 1985,
pp. 452-453.
[7] Brown, W. H. and Miranda, T. J., Official Digest, Vol. 36, No.
475, 1964, p. 92.
[8] Paul, S., Surface Coatings, John Wiley & Sons, New York, 1985,
p. 485.
[9] Sato, K., Progress in Organic Coatings, Vol. 8, No. 1, 1980.
[10] Miranda, T. J., Journal of Paint Technology, Vol. 43, No. 553,
1971, p. 51.
[11] Seymour, R. B. and Carraher, C. E., Jr., Polymer Chemistry, An
Introduction, 3rd ed., Marcel Dekker, New York, 1992, p. 139.
[12] Stevens, M. P., Polymer Chemistry, An Introduction, 2nd ed.,
Oxford University Press, 1990, p. 167.
[13] Miranda, T. J., Mechanical Behavior of Materials, Vol. III, The
Society of Materials Science, Japan 1972, p. 392.
[14] Lambourne, R., Ed., Paint and Surface Coatings, Ellis Horwood
Ltd., 1987, p. 607.
[15] Allcock, H. R. and Lampe, F. W., Contemporary Polymer Chem-
/stry, 2nd ed., Prentice Hall, Englewood Cliffs, NJ, 1990, p. 427.
[16] Myers, R. R., Journal of Polymer Science, C, Vol. 35, No. 3, 1971.
[17] Anderson, J. L., Root, D. E., and Green, G., Journal of Paint
Technology, Vol. 40, No. 320, 1968.
[18] Rossi, A. G. and Paolini, A., Journal of Paint Technology, Vol. 40,
No. 328, 1968.