MNL17-EB/Jun.
1995
Dynamic Mechanical and
Tensile Properties
by Loren W. Hill I
DYNAMICMECHANICALAND TENSILE PROPERTIES are d e t e r m i n e d
in all b r a n c h e s of m a t e r i a l s science. There is a large b o d y of
p u b l i s h e d s t r u c t u r e / p r o p e r t y i n f o r m a t i o n that can be inte-
g r a t e d with coatings r e s e a r c h a n d development. By using
s t r u c t u r e / p r o p e r t y information, coatings chemists can design
a n d o p t i m i z e c h e m i c a l structures of the b i n d e r c o m p o n e n t s
of coatings. Purposeful a n d enlightened f o r m u l a t i o n with
well-designed c o m p o n e n t s m a k e s it possible to o b t a i n desir-
able coatings p e r f o r m a n c e in m a n y cases.
D e t e r m i n a t i o n of d y n a m i c m e c h a n i c a l a n d tensile p r o p e r -
ties requires the use of free films. This r e q u i r e m e n t is a
serious l i m i t a t i o n b e c a u s e many, if not most, of the perform-
ance p r o p e r t i e s of coatings are influenced by coating-sub-
strate interactions. Therefore, tests of coatings intact on their
end-use substrates m u s t be thoughtfully coupled with free
film d e t e r m i n a t i o n s . The practical utility of basic m e t h o d s
d e s c r i b e d in this section is greatly e n h a n c e d w h e n results are
i n t e r p r e t e d in relation to results of adhesion, abrasion, hard-
ness, flexibility, toughness, a n d internal stress tests as de-
scribed elsewhere in the m a n u a l .
D y n a m i c m e c h a n i c a l analysis (DMA) a n d stress-strain
analysis (SSA) of tensile p r o p e r t i e s are c o m p l e m e n t a r y meth-
ods in several ways. DMA involves very small strains, w h e r e a s
SSA involves the m a x i m u m strain that the s a m p l e can with-
stand. Since the small strains used in DMA usually do not
exceed the tensile strength or yield strength of the sample, the
m e t h o d is nondestructive. This feature facilitates p r o p e r t y
d e t e r m i n a t i o n over a wide t e m p e r a t u r e range on a single
sample, that is, DMA is often used as a t e m p e r a t u r e - s c a n n i n g
method. In contrast, SSA d a t a are usually o b t a i n e d at a single
t e m p e r a t u r e , preferably on an i n s t r u m e n t located in a con-
trolled t e m p e r a t u r e a n d h u m i d i t y room. Since the s a m p l e is
b r o k e n in each test, it is very a r d u o u s to c a r r y out SSA over a
wide t e m p e r a t u r e range, a n d SSA is not a m e n a b l e to t e m p e r -
a t u r e scanning.
DEFINITIONS
Tensile Versus Shear Tests
Two types of d e f o r m a t i o n of a b l o c k - s h a p e d s a m p l e are
depicted in Fig. 1. These d e f o r m a t i o n s are used frequently in
p r o p e r t y d e t e r m i n a t i o n s b e c a u s e they can be carried out re-
p r o d u c i b l y a n d treated b y simple m a t h e m a t i c s . In a tension
test (Fig. 1A), the s a m p l e is pulled a p a r t with straight line
IMonsanto Co., Springfield, MA 01151.
Copyright9 1995 by ASTM International
46
a p p l i c a t i o n of force, called "uniaxial extension." In a s h e a r
test (Fig. 1B), one face of the cube is held s t a t i o n a r y a n d the
s a m p l e is p u s h e d sideways by a p p l i c a t i o n of force at the
opposite face. Note that different symbols (e epsilon o r 3~
g a m m a ) are used for strain in these two tests. A single s y m b o l
is used for stress (or sigma), b u t subscripts indicate the type of
test. In Fig. 1, F is force a n d A, B, a n d C are initial s a m p l e
dimensions. The p r o d u c t A • B is the initial cross-sectional
area.
It is evident in Fig. 1 that strain is defined quite differently
in tension a n d shear tests. In a tension test, strain is the
fractional increase in s a m p l e length. In a shear test, strain is
the distance m o v e d by the movable face divided b y s a m p l e
thickness, i.e., the distance between the s t a t i o n a r y a n d mova-
ble faces. In b o t h tests, stress is force divided by cross-sec-
tional area, a n d m o d u l u s is stress divided by strain. Since
strain is unitless, stress a n d m o d u l u s have the s a m e units
(force/area). It is evident in Fig. 1A that cross-sectional a r e a
will decrease as AC increases. If the initial cross-sectional
a r e a is used to calculate or,, the resulting E is called "engineer-
ing" modulus. If the change in cross-sectional a r e a is incorpo-
r a t e d in the calculation, the resulting E is called "true" m o d u -
lus.
The r e l a t i o n s h i p between tensile m o d u l u s a n d s h e a r m o d u -
lus is
E = 2 (1 + v,)G (1)
w h e r e /, is Poisson's ratio [1,2]. F o r m a t e r i a l s that do n o t
u n d e r g o change in volume with strain, /, = 0.5, a n d Eq 1
b e c o m e s E = 3G. Experimentally, /, is very close to 0.5 for
r u b b e r y m a t e r i a l s a n d slightly less t h a n 0.5 for m a n y t h e r m o -
plastic p o l y m e r s [1,2].
Definitions of Dynamic Properties
In d y n a m i c testing, an oscillating strain is applied, a n d the
resulting oscillating stress is measured, or conversely an
oscillating stress is applied, a n d the resulting oscillating
strain is measured. Definitions a n d m a t h e m a t i c a l t r e a t m e n t s
do n o t d e p e n d on w h i c h of these m o d e s of o p e r a t i o n is used.
Relationships b e t w e e n strain, stress, a n d time are sketched in
Fig. 2 for tensile DMA with a p p l i c a t i o n of strain a n d m e a s u r e -
m e n t of stress. The m a x i m u m a p p l i e d strain is %. The maxi-
m u m resulting stress is at.0. Oscillation is d e p i c t e d as a sine
wave, b u t w h e t h e r o r not the driver of the i n s t r u m e n t in use
actually delivers a sine wave oscillation m a y d e p e n d on the
p a r t i c u l a r instrument. The s a m p l e is held u n d e r sufficient
534
www.astm.org
 CHAPTER 46--DYNAMIC MECHANICAL AND TENSILE PROPERTIES 535

T
c I
e
I
I

I
e
I
i!
I I
I

11 I '

L.. _ I~ S
L A d
q

A. TENSILE B. SHEAR

E = Tensile Strain 7 = Shear Strain

at = Tensile Stress as = Shear Stress

A C AX
E ....... 7 =
C C

F F
(3" t ---- Os =

AxB AxB

E = Tensile Modulus G = Shear Modulus

O"t Gs
E = G =
E 7

FIG. 1-Deformations of test samples: A. tensile, B. shear. The two types of deformation
have different definitions and different symbols for strain, stress, and modulus.

tension so that it r e m a i n s taut (not slack) even w h e n the

Tensile Storage M o d u l u s = E' - ~,,o cos8
oscillating strain is at a m i n i m u m . E0 (2)
The sine waves for strain a n d stress have the s a m e fre-
quency, b u t for viscoelastic s a m p l e s the waves are out of Tensile Loss M o d u l u s -- E" - ~r''~sin8 (3)
p h a s e by an a m o u n t , 8, called the phase lag. Theoretically and EO
experimentally, ~ is zero for an ideal (Hookean) elastic solid.
E pr
If an ideal (Newtonian) liquid could be tested in this way, Loss Tangent = - - = tan8 (4)
w o u l d be 90 ~ F o r viscoelastic materials, 8 lies between 0 a n d E'
90 ~ a n d the value of ~ is a r a t h e r direct i n d i c a t i o n of visco- The t e r m "storage" is associated with the elastic p a r t of the
elastic c h a r a c t e r [1-4]. r e s p o n s e E' b e c a u s e m e c h a n i c a l energy input to elastic mate-
Definitions of d y n a m i c p r o p e r t i e s d e p e n d on the concept of rials is "stored" in the sense of being completely recoverable.
resolving the stress wave of Fig. 2 into two waves, one that is The t e r m "loss" is associated with the viscous part of the
in p h a s e with strain a n d one that is 90 ~ out of phase with response E" b e c a u s e m e c h a n i c a l energy input to ideal liquids
strain. The in-phase resolved plot represents elastic response, is totally lost t h r o u g h viscous heating. The ratio E"/E' is
a n d the 90 ~ out-of-phase resolved plot represents viscous re- viscous response expressed relative to elastic response. This
sponse. In terms of modulus, the s e p a r a t e d responses result ratio reduces to sin6/cosS, which is tan& Thus, the n a m e "loss
in the following definitions tangent" is a p p r o p r i a t e .
536 PAINT AND COATING TESTING MANUAL

d In the N e w t o n i a n liquid limit (8 = 90~ 4" is zero b y Eq 9, a n d

I I
, i
' I
Stress (at)
or
Strain (E)
T i m e or Angle
FIG. 2-Applied oscillating strain (~) and resulting oscillat-
ing stress (~rt) in a dynamic mechanical analysis experiment
with tensile deformation. The phase lag (6) and maximum
values of strain (Co) and stress (~rt,o) are indicated.
A check of limiting values of a is consistent with assign-
m e n t of elastic a n d viscous responses in Eqs 2 and 3. W h e n 8
= 0 ~ cos8 = 1.0 a n d sin8 = 0. By Eq 3, E" is zero a n d all of
the response is elastic, i.e., E ' from Eq 2. W h e n 8 = 90 ~ cos8
= 0 a n d s i n ~ -- 1.0. N o w E ' is zero b y E q 2 and all of the
response is viscous, i.e., E ' from Eq 3.
DMA relationships in Eqs 2 a n d 3 relate directly to charac-
terization of s a m p l e s that are solid or semi-solid. Other objec-
tives of DMA include following viscosity a n d elasticity
changes as the cure of t h e r m o s e t coatings takes place a n d
d e t e r m i n i n g the melt-flow p r o p e r t i e s of p o w d e r coatings be-
fore the onset of cross-linking. W h e n viscous response is the
m a i n interest, DMA is often carried out in shear.
The t r e a t m e n t for shear DMA is identical, b u t with selec-
tion of a p p r o p r i a t e s h e a r symbols from Fig. 1, the definitions
arc
S h e a r Storage M o d u l u s = G' - as,0 cos8
To
S h e a r Loss M o d u l u s = G" - ~176sin8
To
G"
Loss Tangent = - - = tan8
G'
Once the e x p e r i m e n t e r s have values of o~,o, T0/and 8 in hand,
it is their choice w h e t h e r to express results in t e r m s of m o d u -
lus values, Eqs 5 a n d 6, or in t e r m s o f " d y n a m i c viscosity." F o r
d y n a m i c viscosity, the frequency of oscillation, to in r a d i a n s
p e r second, is required, b u t this frequency is usually known.
The frequency is required b e c a u s e viscosity is (shear stress)/
(rate of s h e a r strain). In a d y n a m i c s h e a r test, rate of shear
strain is the p r o d u c t to x T. Definitions of d y n a m i c viscosity
are
D y n a m i c Loss Viscosity = 4' - G" _ trs,0 sin8
to toT0
D y n a m i c Storage Viscosity = 4" - G' _ ors,0cos8
to toTo
4'
Loss Tangent = - - = t a n a
4"
all of the response is viscous, 4' from Eq 8. F u r t h e r m o r e in
this limit, G' is zero by either Eq 9 or Eq 5, a n d the viscous
response could alternatively be expressed in t e r m s of G" from
Eq 6. Thus, in d y n a m i c shear tests, m o d u l u s a n d viscosity
d e t e r m i n a t i o n s are one a n d the s a m e experiment. Usually
e x p e r i m e n t e r s will choose Eqs 5 a n d 6 w h e n the s a m p l e has a
lot of elastic c h a r a c t e r and only a little viscous character,
w h e r e a s the logical choice for m a i n l y viscous m a t e r i a l s hav-
ing only a little elastic c h a r a c t e r will be Eqs 8 a n d 9. In
principle, it w o u l d be valid to express tensile DMA results in
t e r m s of d y n a m i c viscosities as well. This is not done very
often, p r o b a b l y b e c a u s e viscosity is strongly associated with
shearing experiments, not with tensile experiments. The close
association of viscosity with shear is the basis for o m i t t i n g
the w o r d "shear" at the left in Eqs 8 a n d 9.
The relationships between m o d u l u s values defined in Fig. 1
a n d the d y n a m i c m o d u l u s values are [ 1 - 4 ]
E 2 = E '2 + E "2 (11)
G 2 = G '2 + G "2 (12)
Use of complex n u m b e r s a n d quantities such as i =
has been avoided here. If r e a d e r s w o u l d like definitions of
such quantities as the "complex tensile storage modulus," E*,
they should consult Refs 1 - 4 . Complex n o t a t i o n m a y be con-
venient for m a t h e m a t i c a l derivations, b u t complex m o d u l u s
values, with their i m a g i n a r y parts, a d d little or nothing to the
i n t e r p r e t a t i o n of s t r u c t u r e / p r o p e r t y relationships.
Definitions of Tensile Properties
The t e r m "tensile properties" logically refers to all proper-
ties that can be d e t e r m i n e d in tests that involve tensile defor-
m a t i o n as d e p i c t e d in Fig. 1A. C o m m o n tests t h a t involve
tensile d e f o r m a t i o n include stress-strain tests, creep tests,
a n d stress relaxation tests. Stress-strain tests are used m u c h
(5)
m o r e frequently t h a n the others. Therefore, the t e r m s "tensile
properties" a n d "stress-stain properties" are often used inter-
(6) changeably. Creep a n d stress-relaxation tests are s o m e t i m e s
referred to as "transient tests" b e c a u s e responses, either elon-
gation or stress, change with t i m e and are d e t e r m i n e d as a
(7) function of t i m e [5].
Terminology, definitions, a n d symbols for stress-strain
tests have been taken from a n earlier edition of the P a i n t
T e s t i n g M a n u a l [6] a n d from several ASTM standards:
D 2370 Test M e t h o d for Tensile Properties of Organic
Coatings
D 638M Test M e t h o d for Tensile Properties of Plastics
(Metric)
D 882 Test M e t h o d for Tensile Properties of Thin Plas-
tic Sheeting
D 412 Test Methods for Vulcanized R u b b e r a n d Ther-
m o p l a s t i c R u b b e r s a n d T h e r m o p l a s t i c Elasto-
(8) mers--Tension
D 883 T e r m i n o l o g y Relating to Plastics
In a stress-strain test, the s a m p l e is elongated at c o n s t a n t
(9)
rate. The force, also called "load," required to m a i n t a i n con-
stant rate of elongation is determined. Force is converted to
(10) tensile stress (~rt) b y division by the initial cross-sectional a r e a
(A X B in Fig. 1A). Results are p r e s e n t e d as a plot of stress (trt)
 C H A P T E R 4 6 - - D Y N A M I C M E C H A N I C A L AND T E N S I L E P R O P E R T I E S 537

on the vertical axis versus strain (either ~ or 100 • E = % /llll//f STRESS RELAXATION EXPERIMENT
elongation) on the horizontal axis. A hypothetical example is
shown in Fig. 3 [5, 6]. The tensile modulus (E) is the slope of E I" : RELAXATION TIME
the initial, linear portion of the plot (see Fig. 3). If the initial
CREEP EXPERIMENT
part of the plot is not linear, several calculations for esti-
mating E have been suggested in ASTM D 638M. Use of the 1" = RETARDATION TIME
slope for E amplifies the simple definition of tensile modulus 17
given in Fig. 1A. Other terms used for tensile modulus include
"elastic modulus," "Young's modulus," and "stiffness." d T =

The first point on the plot of Fig. 3 where the slope is zero is E
called the "yield point." Strain at the yield point is called FIG. 4 - A mechanical model consisting of a spring and a
"elongation at yield" (ey). Stress at the yield point is called dashpot permits definition of relaxation time and retardation
"yield strength" (err). Elongation is continued until the sam- time,
ple breaks. Strain at the break point is called "elongation at
break" (eB). Stress at the break point is called "tensile
divided by the modulus of the spring. Tau has units of time.
strength" (%) as shown in Fig. 3. However, in some cases Results of the creep experiment for the Maxwell model can be
(not shown) the stress is higher at the yield point than it is at
expressed as
the break point. In such cases, ASTM standards specify that
the "tensile strength" be indicated as the higher value of stress ~(o)
E(t) = e(0) + t (13)
and be designated as "tensile strength at yield." Practice is not q-

uniform with regard to this latter "tensile strength" terminol-

ogy. When stress is first applied, the spring extends instanta-
neously by an a m o u n t ~(0). Then retarded further elongation
Results of transient tests have not frequently been pub-
takes place due to flow in the dashpot. It is evident in Eq 13
lished for coatings. Such tests clarify viscoelastic character
quite directly. Possibly unexpected field failures of coatings that the retarded elongation is linear with time. The value of r
can be obtained from the product (reciprocal of the slope) •
could be avoided in some cases if more attention were given
(intercept) [4,5].
to viscoelasticity. Only the most simple form of retardation
In a tensile stress relaxation experiment, the sample is
and relaxation concepts are treated here.
elongated instantaneously by an a m o u n t ~, and thereafter ~ is
In a tensile creep experiment, the sample is subjected to
held constant. Stress is determined as function of time, tr(t).
constant stress, or,, and elongation is determined as a function
Analysis of the dependence of stress on time yields "relaxa-
of time, e(t). Analysis of dependence of elongation on time
tion time," r. For the Maxwell model, T values are the same
yields "retardation time," T (tau). The simplest mechanical
whether from creep or relaxation. For real materials, experi-
model that permits definition of T is the Maxwell model as
mentation is required to determine whether or not retarda-
shown in Fig. 4. This model consists of a series connection of
tion and relaxation values are equal. Results of the stress
an ideal Hookean spring of modulus, E, and a dashpot that
relaxation experiment for the Maxwell model can be ex-
contains an ideal Newtonian liquid of viscosity, r/. As indi-
pressed as
cated in Fig. 4, ~-is the viscosity of the liquid in the dashpot
or(t) = o(0)e t/T (14)
When the instantaneous elongation is applied, the time zero
response is entirely in the spring. Then the dashpot extends
with time relieving stress on the spring. It is evident from Eq
14 that the value of r can be obtained as the time at which
P OB stress has been reduced to 1/e (0.368) of its initial value.
0u Alternatively, one can obtain the value of -r from the negative
(9
U of the reciprocal of the slope of a plot of In a(t) versus t [4,5].
t-
O To represent mechanical response of viscoelastic poly-
meric materials, it is usually necessary to use more elaborate
(/)
(/~ mechanical models and to replace a single value of r by "a
LU spectrum of relaxation times" [1,2].
IZ
I--
O~

PREPARATION OF FREE FILM SAMPLES

.I Methods for preparation and cure of adherent films are
Ey EB
described elsewhere in the manual and in ASTM Test Meth-
STRAIN ods for Producing Films of Uniform Thickness of Paint, Var-
FIG. 3 - A hypothetical stress-strain curve for a ductile nish, and Related Products on Test Panels (D 823-87). Since
film. Tensile properties are defined: tensile modulus (E), dynamic mechanical and tensile property determinations re-
elongation at yield (ey), elongation at break (eB), yield stress quire free films, ASTM Practice for Preparation of Free Films
(~ry), and tensile strength (~rB). of Organic Coatings (D 4708-87), is also very useful. Details
538 PAINT AND COATING TESTING MANUAL
concerning thickness measurements, which are required for
calculation of cross-sectional area, are given in ASTM Test
Method for Measurement of Dry-Film Thickness of Organic
Coatings Using Micrometers (D 1005).
The most widely used method for free film preparation
involves application on release substrates, i.e., low surface
energy substrates. Four release substrates are described in
ASTM D 4708-87. Low surface energy results in poor adhe-
sion so that the coating can be stripped from the release
substrate after it is cured. Surface tension differences be-
tween the coating and release substrate must be carefully
balanced. If the surface tension of the liquid coating is higher
than the critical surface tension of the release substrate, the
coating will crawl inward from the edges to give nonuniform
thickness. In extreme cases of crawling, the coating will break
up into unconnected puddles.There are many types of release
paper and many surface treating agents to convert glass or
metal panels into low-energy surfaces. It is worthwhile to try
several release surfaces to find the balance which will avoid
crawling but will still permit separation. Tendency to crawl
can be reduced by use of high-viscosity formulations. Viscosi-
ties for draw-down application (see ASTM D 823-87) can be
quite high compared to those required for spray application.
The second most widely used method for preparation of
free films involves amalgamation of tin by mercury. ASTM D
4708-87 describes use of 25-1xm-thick dental tin foil. The foil
is smoothed onto glass plates before application of the coat-
ing. In our laboratory we have used 7.6 by 15.2-cm (3 by 6-in.)
tin-plated steel panels (Type DT panels, Q-Panel Co.) The tin
plate on the panels amalgamates much more quickly than
that on tin-plated food can stock. After the coating is cured,
the panel is placed in a wide-mouth quart jar containing
mercury to a depth of only 0.64 to 1.3 cm (1/4 to 1/2 in.). The
jar is tightly capped during amalgamation. During a period of
one and one half to two days, mercury creeps up the panel
underneath the coating as tin is amalgamated. After the film
is completely freed from the substrate, it can be lifted off and
wiped to remove mercury. The amalgamation procedure is
best carried out in a hood reserved for this purpose. The work
surface of the dedicated hood can consist of a metal grid
mounted 1.3-cm (1/2 in.) above a shallow tray that contains
sulfur. Other safety precautions include careful attention to
panel handling procedures and disposal procedures, frequent
monitoring of air flow velocities, use of protective gloves, and
mercury vapor monitoring devices. Danger of exposure to
mercury vapor has resulted in prohibition of amalgamation
methods in some coatings laboratories.
Thickness is an important consideration in preparation of
samples for dynamic mechanical and tensile property tests.
Usually tests are more reproducible if samples are thicker
than normal coatings thicknesses. However, film formation
seldom occurs in exactly the same way for thick films as for
thin ones. Several reasons for dependence of cured film prop-
erties on thickness have been discussed [5]. In our laboratory,
films of 1 mil (25 ~m) and up have been analyzed routinely. It
has not been possible to analyze or even handle very thin free
films such as beverage can coatings which are approximately
3 to 5 /zm thick.
Coatings and thin plastic film samples are usually prepared
as rectangular strips, whereas thicker materials are prepared
as dogbone-shaped samples. The narrowing in the middle of
the dogbone tends to control where failure occurs in tension
tests, but for thin samples this narrowing causes the cross-
sectional area to be too small for many load measuring cells.
The dogbone shape also provides more area for clamping
which facilitates the balance between slip-free clamping and
avoidance of rupture at the clamp.
There is extensive literature on the notch sensitivity of poly-
meric materials in stress-strain tests [7]. The challenge in
preparation of high Tg coating samples is to avoid undesired
notches, nicks, or cracks along the edges. Small edge cracks,
which are very difficult to detect even with magnification, can
cause premature failure in tension tests. Usually samples are
die cut, and the sharpness and condition of cutting edges of
the die affect uniformity of sample edges.
D E T E R M I N A T I O N OF D Y N A M I C
PROPERTIES
Description of Dynamic Mechanical Analysis
(DMA)
One of the reasons for rapidly expanding use of DMA for
coatings and other research is the availability of automated
and computer-controlled instrumentation. Automated in-
struments and the suppliers of these instruments are listed in
Table 1 [4]. A common feature of all these instruments is
oscillatory deformation, an example of which is shown in Fig.
2. Variable features include: the type of deformation (tensile,
shear, or poorly defined), free versus forced oscillation, fre-
quency scan versus temperature scan versus either, sensitiv-
ity for thin film analysis, capability of transversing the entire
range of property behavior (glassy to transition to rubbery)
during a single temperature scan, breadth and rate of temper-
ature scan, breadth and rate of frequency scan or range and
number of frequency settings, versatility of sample holding
devices, ruggedness versus flimsiness, amount of attention
required once a run has been started, accuracy and versatility
of the associated software for control during the run and data
treatment and plotting after the run. In several cases, newer
models permit determination of properties at several fre-
TABLE 1--Automated DMA instruments.
CSL Rheometer--Carri-Med
Dynamic Mechanical Analyzer, DMA 442--Netzsch
Dynamic Mechanical Analyzer, DMA 7--Perkin-Elmer
Dynamic Mechanical Analyzer, DMA 983--TA Instruments
Dynamic Mechanical Rheological Inst., RPA 2000--Monsanto
Dynamic Mechanical Thermal Analyser--Polymer Labs
Dynastat/Dynalyzer--Dynastatics/Imass
Mechanical Spectrometer; RMS 800, RDS II, RDA--Rheometrics
Rheolab MC 20--Physica
Rheovibron/Autovibron--Imass
Rheovibron DDV-II-C,Automated--Orientec
Servo-Hydraulic Machine--Instron
Solids Analyzer, RSA II--Rheometrics
Torsional Braid Analyzer--Plastics Analysis Instruments
Torsionautomat--Brabender
Viscoanalyser--Indikon/Metravib
VOR Rheometer--Bohlin
Weissenberg Rheogoniometer--Carri-Med
NOTE:In addition, severalthermo-mechanicalanalysisinstruments havean
option of oscillatoryloading of the TMAprobe.
 CHAPTER 4 6 - - D Y N A M I C MECHANICAL AND TENSILE PROPERTIES
quencies during a single temperature scan. Although it is
necessary to use a rather low temperature scan rate in multi-
ple frequency runs, the a m o u n t of data obtained is remark-
able. Chances of acquiring an instrument that will actually
function well in the intended experiments are greatly in-
creased by asking suppliers about these variable features.
The procedure for carrying out a DMA run on an auto-
mated instrument is rather simple, with details depending on
the particular instrument. Usually the associated software
includes a "run" p r o g r a m which prompts the operator to
input sample data (e.g., thickness) and settings for the run
such as initial and final temperatures, frequency of oscilla-
tion, heating rate, etc. After the input steps, there is usually a
cooling period. The instrument takes over when the preset
initial temperature is reached. Thereafter nothing is required
of the operator until the run is finished. Usually initial and
final temperatures are selected to span the glassy region,
transition region, and rubbery plateau region. For direct ten-
sile DMA, the run program usually contains a tensioning sub-
routine, which provides constant static tension sufficient to
avoid slack in the sample in the glassy region and then de-
creasing static tension as the sample softens in the transition
region. Modification of the tensioning sub-routine is often
necessary. If tension is too high, films break in the glassy
region or are pulled apart in the transition region. If tension
is too low, slack results or the oscillatory stress falls below
measurable values. Skilled operators soon develop several
modified run programs with different tensioning parameters
that are suitable for samples of various properties and dimen-
sions.
Various support materials, such as glass braids and metal
springs or shims, are used when the sample is a viscous liquid
and the objective is to follow cure as the coating formulation
is converted to a solid. Use of supports makes it difficult to
obtain absolute values of E', but relative values are often
sufficient for c o m p o n e n t optimization. The position of peaks
in E" or tan8 plots are usually not shifted when a support is
used. When coating samples do not contain solvents, e.g.,
powder coatings and 100% active coatings, parallel plate, and
cone and plate geometries can be used.
In some cases, DMA is treated as an adjunct to
thermomechanical analysis (TMA). The TMA probe is driven
up and down in an oscillatory m a n n e r as temperature is
scanned. General indications of liquid-like character during
transitions can be obtained, but quantitative DMA data are
not often obtainable in this manner.
Interpretation of DMA Plots
DMA plots are shown in Fig. 5 for a clear film prepared
from an acrylic polyol (ACR) and an etherified melamine
formaldehyde (MF) cross-linker. Plots are labeled according
to Eqs 2, 3, and 4. The storage modulus level at the left is
typical of amorphous, unpigmented films in the glassy state.
The 25~ data are of interest for comparison with modulus
values obtained from the slope of stress-strain plots because
SSA is usually carried out at 25~ The value of E' (25 ~ from
the computer printout corresponding to Fig. 5 is 1.38 • 101~
dynes/cm 2. The same value expressed in other units is 1.38 •
109 Pa or 2.00 • l0 s psi (1 pascal = 1 newton/m 2 -- 10 dynes/
c m 2 = 1.45 • 10 -4 pounds-force per square inch). The
539
r e c o m m e n d e d SI unit is Pa. The value of E" (25 ~ is 6.86 x 108
dynes/cm 2. Inserting E' and E" (25 ~ values into Eq 11 and
solving for tensile modulus, E, we obtain E = 1.382 • 101~ In
this case E = E' (25 ~ to a very close approximation, and the
contribution of E" (25 ~ to E is negligible. Hard, tough coat-
ings often have tensile modulus values from SSA ranging
from 1 • 101~ to 3 • 10 l~ dynes/cm 2 [5,7,8], in agreement
with the DMA value. For a quantitative comparison of E from
SSA and E from DMA via Eq 11, the strain rate from SSA
would have to be matched with the oscillating frequency
from DMA.
The viscous response is not always negligible relative to
elastic response, of course. The E" contribution is highest at
the temperature of the m a x i m u m in tan delta, 79~ in Fig. 5.
Note that E' (79 ~ is 1.04 • 109 dynes/cm 2, a n d E " (79 ~ is 5.15
• 108 dynes/cm 2. F r o m Eq 11, E = 1.16 • 109 dynes/cm 2,
and E > E' (79 ~ for this case. If we actually carried out SSA at
79 ~and a strain rate corresponding to 11 Hz, we would expect
to find E = 1.16 • 109 dynes/cm 2. During the elongation in
SSA it would not be evident that a significant fraction of the
resistance was viscous in nature. However, after the sample
broke or was released from the grips, retraction would be
delayed (not instantaneous) and part of the deformation
would be permanent.
The middle portion of the plots in Fig. 5 represents the
transition region where E' drops sharply and both E" and
tan8 go through a maximum. The glass transition tempera-
ture, Tg, is usually taken as the temperature of the m a x i m u m
in the tan8 plot, 79 ~ in Fig. 5. Some users of DMA prefer to
define the temperature of the m a x i m u m in the E" as Tg, 55 ~ in
Fig. 5. The lower Tg value agrees more closely with that
obtained from differential scanning calorimetry, but the
higher value can be obtained with better reproducibility be-
cause the tan8 peak is sharper than the E" peak. Regardless of
the data point selected to express Tg, it is important to re-
m e m b e r that Tg depends on rate of testing for viscoelastic
materials.
The effects of changing rate of testing, i.e., frequency in
DMA, are shown in Table 2. The 11 Hz data of Table 2
correspond to the run depicted in Fig. 5. A ten-fold increase in
frequency results in a 7 to 9 ~ increase in Tg with a slightly
stronger dependence on frequency at the higher frequencies.
In a recent review, H a r t m a n n [9] noted that a 7~ Tg change
per decade change in frequency is used as a "rule-of-thumb."
Results of Table 2 are consistent with this generalization. The
height of the tan6 peak is nearly independent of frequency,
but the width increases with increasing frequency. Very simi-
lar dependence of height and width on frequency was ob-
served for lightly cross-linked epoxy films [9]. Values of E'
(min) increase slightly with increasing frequency (Table 2).
The structural implications of E' (min) will be discussed in
the next sub-section.
Height and width of tan8 peaks reflect structural homoge-
neity and cross-link density. Homogeneous, uncross-linked,
noncrystalline polymeric materials of narrow molecular
weight distribution usually have tan8 (max) values greater
than one and sometimes greater than two. Such tan8 peaks
are very narrow. A broader molecular weight distribution
results in a wider peak and a lower value of tan8 (max).
Introduction of cross-links invariably reduces tan8 (max) and
usually increases peak width. For homogeneous cross-linked
540 P A I N T AND COATING T E S T I N G M A N U A L

11

STORAGE MODULUS

oo

I--
bJ
-1 ~
/
"8 LOSS T A N G E N T

'7
w I i o o i ! I I 1 i i i i i i ! I ~

o o o o o o o o o o

TENPERATURE (C)
FIG. 5 - D M A plots for a clearcoat prepared from an acrylic polyol (ACR) and an etherified
melamine formaldehyde (MF) resin, ACR/MF 70/30. The film was cured before DMA for
30 min at 120~ with 0.5% para-toluenesulfonic acid. DMA was carried out at 11 Hz. See
Table 2 for dynamic properties.

TABLE 2--Dynamic properties of acrylic/MF clearcoat.

Frequency, TanS, PW,a E', ( m i n ) , Temperature of E'
Hz Tg, ~ max A, ~ dynes/cm2 (rain), ~
3.5 76 0.49 45 3.3 X l0 s 108
11.0 79 0.49 50 3.6 X 108 112
35.0 83 0.52 55 4.2 X 108 116
110.0 88 0.52 59 4.7 x l0 s 121
aPWis peak width at half height.

samples, peak width reflects the broadness of the distribution
of lengths of chains between junction points in the network
[2,3]. For sound and vibration damping, materials with both
high and wide tan6 peaks would be desireable, but height and
width cannot be adjusted independently [9]. High peaks tend
to be narrow, and wide peaks tend to be low. These observa-
tions have resulted in speculation concerning a general com-
parability of peak areas of the glass transition. Eventually
theoretical treatment of peak areas may prove to be useful for
structure/propert3) correlations.
Samples that undergo partial phase separation during mo-
lecular weight buildup and cross-linking often have very
broad transitions [4,9,10]. Manson and Sperling [10] have
described the use of interpenetrating polymer networks to
limit and control the extent of phase separation. When Tg
values of the separate domains are close to one another, a
general broadening is observed. When Tg values of the sepa-
rate domains are considerably different, tan6 plot shapes
provide considerable structural information. Observation of
two narrow peaks with low tan6 values between them indi-
cates distinct phase separation with little mixing at domain
boundaries. Observation to two broad and indistinct peaks
with high tan6 values between them indicates diffuse do-
mains with extended regions of varying composition at the
boundaries [4,10]. Diffuse domains have also been created in
multiblock uncross-linked polymers, and block design has re-
sulted in controlled broadening of tan6 peaks [11].
The relationships between transition width and coating
end-use performance have been presented for radiation-
cured coatings [12], polyol/melamine thermoset coatings
[13,14], gel coats [14], and can coatings [14]. Although the
glass transition is emphasized in this section, many polymers
are known to have multiple transitions. Low-temperature
transitions are observed in DMA as tan6 or E" peaks that are
quite small compared to the glass transition peaks. As dis-
cussed in the section entitled Relationship to Other Me-
chanical P r o p e r t i e s , good impact resistance is often attrib-
uted to transitions that produce low-temperature loss peaks.
Interpretation of tan6 peak broadening in terms of
structural nonuniformity requires considerable restraint he-
cause in some cases broadening is caused by physical or
chemical changes that take place during the temperature
scan. In some cases, DMA has its own uncertainty principle;
the structural features that are under study are changing
during the determination. Physical changes include loss of
plasticizer or absorbed water and morphological changes
 CHAPTER 4 6 - - D Y N A M I C MECHANICAL AND TENSILE P R O P E R T I E S
such as partial crystallization. Chemical changes include ad-
ditional cross-linking of t h e r m o s e t coatings during the scan
a n d oxidative or t h e r m a l degradation. In general, if the tem-
p e r a t u r e of processing the samples is well above the t e m p e r a -
ture of the tan8 p e a k u n d e r analysis, there is m u c h less
c h a n c e that p r o p e r t i e s are c h a n g i n g d u r i n g the scan.
Determination of Cross-Link Density
F o r u n p i g m e n t e d , cross-linked coating films, the level of
storage modulus, E', in the r u b b e r y plateau region above Tg is
an i n d i c a t i o n of cross-link density. A wide range of variation
has been observed from a p p r o x i m a t e l y 4 x 107 dynes/cm ~ for
lightly cross-linked films to a p p r o x i m a t e l y 2 x 109 dynes/cm 2
for very highly cross-linked films. Increases in E' values in the
r u b b e r y p l a t e a u have b e e n a t t r i b u t e d to increases in cross-
link density for m a n y types of studies: increasing cure tem-
p e r a t u r e a n d cure t i m e [13,16-18], increasing r a d i a t i o n dose
in electron b e a m curing [15], increasing the s t o i c h i o m e t r i c
b a l a n c e in epoxy films [2,19] a n d in p o l y o l / m e l a m i n e films
[13,17,18], increasing the functionality of the cross-linker in
r a d i a t i o n cure films [20] a n d in p o w d e r coatings [21,22], a n d
increasing the m o l e c u l a r weight of the m a i n film former in
acrylic clearcoats [23].
Quantitative aspects of the relationship between E' in the
r u b b e r y p l a t e a u and cross-link density have recently been
clarified [18]. Cross-link density is defined as
v~ ~ moles of elastically effective n e t w o r k chains (15)
p e r cubic c e n t i m e t e r of film
Cross-link density can be calculated using Eq 16
G' E'
ve - - (16)
RT 3RT
where the storage m o d u l u s values, G' or E', are o b t a i n e d in
the r u b b e r y plateau, T is t e m p e r a t u r e in degrees K corre-
s p o n d i n g to the storage m o d u l u s value, a n d R is the gas
constant (8.314 x 107 dynes/degrees K 9 mole in the cgs unit
system). Inserting the 3.5 Hz d a t a from Table 2 (E' = 3.3 X
108 dynes/cm 2 a n d T = 108~ = 381~ into Eq 16 gives Ve =
3.47 X 10 -3 moles/cm 3. Since Eq 16 has no c o r r e c t i o n for
frequency d e p e n d e n c e of E', a m o r e a c c u r a t e value w o u l d be
o b t a i n e d if frequency were r e d u c e d until E ' no longer de-
p e n d e d on frequency. E x t r a p o l a t i o n to zero frequency was
used in cross-link density calculations for p o w d e r coatings
[21]. F o r a p o l y u r e t h a n e film of low Tg b u t relatively high
cross-link density, E ' plots were identical in the r u b b e r y pla-
teau at 11 a n d 110 Hz [18]; thus, no frequency e x t r a p o l a t i o n
was necessary for this case.
E q u a t i o n 16 has b e e n called "the ideal n e t w o r k law" with
an analogy i m p l i e d to the ideal gas law [18]. In an ideal
network, all chains are elastically effective. Conversion in the
n e t w o r k f o r m i n g reaction is complete, a n d there are no small
loops or dangling ends. F o r ideal networks f o r m e d by func-
tional group reactions of t e r m i n a l l y functional (telechelic)
starting materials, the value of Ve can be calculated directly
from Eq 15. The calculation requires only a b a l a n c e d chemi-
cal equation a n d an e x p e r i m e n t a l d e t e r m i n a t i o n of c u r e d film
density. F o r example, c o n s i d e r a tetrafunctional core-
actant B 4 (M n = 3000) cured by a trifunctional cross-linker
A3 (M~ = 300)
541
4A 3 + 3B 4 ~ I d e a l N e t w o r k (density = 1.10g/cm 3)
The m a s s of the n e t w o r k f o r m e d b y this r e a c t i o n is 10 200 g (3
x 3000 + 4 x 300), a n d the volume is 10 200/1.10 = 9273
c m 3. This volume of cured film contains 24 tool of chain ends
(4 x 3 + 3 x 4 ) c o m i n g into j u n c t i o n points in the network.
By definition, a chain has two ends; therefore, there are 12
tool of elastically effective chains in 9273 c m 3 of ideal net-
w o r k film. F r o m Eq 15, Ve = 12/9273 = 1.29 X 10 -3 mo1/cm 3.
E q u a t i o n 17, a t t r i b u t e d to Scanlon [18,24], formalizes this
type of calculation
v~
=3 4 5
-~C3 + 2 C4 + ~C5 + . . . . .
1
~fcf
21.=3
(17)
where Cf is the concentration of "f" functional reactant ex-
pressed in unusual units, i.e., moles of reactant per cubic
centimeter of final film. Difunctional reactants contribute to
v o l u m e b u t do not increase the n u m b e r of moles of chains.
Therefore, there is no C2 t e r m in Eq 17.
Ideal n e t w o r k calculations have been carried out for sev-
eral types of coatings such as polyester p o l y o l / m e l a m i n e films
[17], epoxy/diamine films [19], and p o w d e r coating films
[21,22]. The ue values calculated from r e a c t a n t structures
agree r e m a r k a b l y well with e x p e r i m e n t a l Ue values from Eq
16.
Although v~ is useful for n e t w o r k characterization, m o s t
coating chemists can m o r e easily visualize a n e t w o r k b a s e d
on the value of Mc
M c = weight of s a m p l e in g r a m s that contains one (18)
m o l e of elastically effective chains
If chain lengths in the n e t w o r k vary, one can place a b a r over
M c a n d refer to this quantity as " n u m b e r average m o l e c u l a r
weight of effective n e t w o r k chains." Based on Eqs 15 a n d 18,
the relationship b e t w e e n ue a n d Mc is
Mc- p (19)
v~
w h e r e p is film density in g/cmL F o r the 4A3 + 3B 4 example,
Mc = 1.10/1.29 • 10 -3 = 853 g/tool. F o r the film of Table 2,
the experimental density is 1.12 g/cm 3, and Mc is 1.12/3.47 •
10 -3 = 323 g/tool. Of course, a high value of Mc c o r r e s p o n d s to
a loose n e t w o r k a n d a low value to a tight network.
E q u a t i o n 16 can be c o n s i d e r e d e m p i r i c a l or the result of
kinetic theory of r u b b e r elasticity [20,24-28]. The theory was
developed for networks that have very long chains between
j u n c t i o n points. F o r long chains, c o n f o r m a t i o n s can be
treated by statistical-mechanics concepts. The chains in net-
works of greatest interest for coatings are m u c h too short for
such treatments. F o r long chains between j u n c t i o n points,
results of the theory are often expressed as [20]
G
re= Vc + Up gRT (20)
where ve is s u m of a chemical contribution, vc, a n d a physical
contribution, up. The physical c o n t r i b u t i o n is attributed to
chain e n t a n g l e m e n t s [28] o r physical constraints [25-27].
The factor, g, is related to j u n c t i o n p o i n t d i s p l a c e m e n t u n d e r
stress a n d is r e p o r t e d to d e p e n d on functionality [20,25]. If
the r e a d e r chooses to use r u b b e r elasticity theory, Eq 16 is
542 PAINT AND COATING TESTING MANUAL
obtained from Eq 20 w i t h g = 1.0, G = G', and vp = 0
(relative to vc).
A new theory is needed that results in Eq 16 by consider-
ation of entropy of conformations of short chains. This ap-
proach would avoid applying long chain theory to material
having short chains.
Relationship to Other Mechanical Properties
Knowledge of dynamic properties is useful for optimizing
the chemicaJ structure of coatings components. When the
binder is a copolymer, monomer ratios can be altered to
control Tg. In thermosets, increasing the functionality of the
cross-linker is expected to cause an increase in cross-link
density. DMA is a very direct method for determining
whether purposeful structural changes have actually had the
desired effects.
In addition to general structure/property uses of DMA,
progress is being made in establishing relationships between
dynamic properties and the results of paint test methods for
hardness, flexibility, impact resistance, and solvent resist-
ance. DMA has some inherent limitations in the establish-
ment of these property/property relationships. The oscil-
latory deformation, e.g., e0 in Fig. 2, is very small. If the paint
performance property depends critically on large deforma-
tions, a property/property correlation should not be expected.
Results of paint performance tests usually depend to some
extent on interactions between coating and substrate. When
dependence on coating-substrate interactions is dominant, a
free film method such as DMA should not be expected to
correlate with results of paint tests.
DMA has helped elucidate the causes of reversals in rank
order of hardness among films when different tests are used
[5,29]. As described elsewhere in the manual, hardness is
determined by penetration, pendulum, and scratch test meth-
ods. The most important property for influencing hardness is
Tg. However, even for a series of films that have the same Tg,
considerable differences are sometimes observed in hardness
test results. We have observed that penetration hardness de-
pends more directly on the E ~(25 ~ value than on Tg. Films of
the same Tg can have quite different values of E' (25~ Pendu-
lum hardness depends more directly on E" values than on E'
values. This result is expected because damping of the swings
of a pendulum depends on conversion of mechanical energy
into heat through viscous effects in the coating. As noted
earlier, E" is a measure of viscous response. Films which have
nearly the same E' (25 ~ values and the same penetration
hardness can have quite different E" (25 ~ values and quite
different values of pendulum hardness. The back and forth
rolling motion of a Sward Rocker is also damped by viscous
effects, and therefore depends strongly on E" values. In this
case, there is also a contribution from sliding friction. Usually
pendulum hardness is determined at a single temperature,
but Sato [29] describes studies of damping time as a function
of temperature. Plots of the reciprocal of damping time ver-
sus temperature have exacdy the same shape as the tan8 plot
for the same films. Both glassy and rubbery materials have
low tan~ values as shown in Fig. 5. If a pendulum hardness
test is carried out at room temperature on a material that is in
its rubbery region at room temperature, a careless interpreter
of results is likely to conclude that rubber is very hard. This
example illustrates that DMA can be used to understand the
results of paint tests more fully.
Among the many scratch tests that have been devised, the
most widely used is pencil hardness. Although pencil hard-
ness results are quite reproducible when carried out by one
skilled in the art, these results sometimes do not correlate
with either penetration or pendulum hardness results. Fur-
thermore, there is no known dynamic property that corre-
lates well with pencil hardness. The plowing action involved
in pencil hardness failures may involve large localized defor-
mations. A relation to stress-strain analysis, which involves
large deformations, is more likely.
Flexibility of coatings is often measured by mandrel bend
tests and falling weight impact tests (see a previous chapter in
this book). In thermoplastic polymer studies, good flexibility
and impact resistance are often associated with low tempera-
ture peaks in E" and tan8 plots [30]. Rubber-toughened epoxy
coatings clearly show the low temperature peak attributable
to the rubber phase [31]. Polyester/melamine films have
much better mandrel bend performance than do acrylic/mel-
amine films of similar Tg and cross-link density. DMA scans
beginning at - 100~ show a weak tan6 peak at - 70~ for the
PE/MF films, but no such peak is observed for the ACR/MF
films [18]. In some cases [12,13], extreme broadening of the
peak in the E" plot has been associated with improvements in
flexibility of coatings.
Pigments often increase the toughness of coatings without
broadening the transition or introducing low-temperature
loss peaks [15]. The main effect of increasing pigment volume
content (PVC = 0 to 55%) on DMA plots is to increase E'
values moderately in the glassy region and strongly in the
rubbery plateau [15]. Values of Tg often increase by about 5 to
10~ at PVC = 0.4 relative to the corresponding clear coat-
ings [15].
Solvent resistance as measured in methyl ethyl ketone dou-
ble rub tests is related to E' values in the rubbery plateau, i.e.,
to cross-link density [5,13]. MEK resistance also depends on
the solubility parameter of the coating. Although the double
rub test is widely used to determine the degree of cure of
thermoset coatings, the only ASTM method adopted relates
to zinc-rich primers (D 4752-87). Relationships between the
number of double rubs and E' (rain) values are quite repro-
ducible within a coating type but not from type to type. For
example, with acrylic clearcoats, 200 double rubs are ob-
tained when E' (min) = 2 • 108 dynes/cm 2 [13]. Films of this
type having 50 to 100 double rubs typically have E' (min)
values in the range of 5 • 107 to 1 to l0 s dynes/cm 2. In
contrast, polyester polyol powder coatings, cured with sev-
eral types of cross-linkers, yielded 200 + double rubs despite
having E' (rain) values as low as 5 • 107 dynes/cm 2 [22]. The
lack of generality in the relationship of MEK resistance to E'
(min) for various coatings types is believed to result in part
from differences in solvent-polymer interactions. There may
also be a weak dependence of MEK resistance on Tg as well as
a strong dependence on E' (rain).
 CHAPTER 46--DYNAMIC MECHANICAL AND TENSILE PROPERTIES
D E T E R M I N A T I O N OF T E N S I L E
PROPERTIES
Description of Stress-Strain Analysis (SSA)
Instrumentation for SSA is described in detail in the ASTM
test methods listed in the section of this chapter entitled
Definitions of Tensile Properties. In most cases, specific in-
struments are not identified, apparently to avoid commercial
implications, but it is generally known than Instron | instru-
ments (Instron Engineering Corp.) are widely used. For or-
ganic coatings the most suitable test method is usually ASTM
D 2370. However, other tension test methods contain addi-
tional useful information. ASTM D 638M is useful for selec-
tion of metric units and units consistent with SI recommen-
dations. ASTM D 882 has rather extensive data on statistical
treatments for plastic sheeting, but the statistical methods
could be beneficially applied to coatings films. For certain
types of coatings, such as flexible primers or coatings for
plastic substrates, rubbery behavior is expected, and ASTM D
412 provides useful information such as data treatment when
a crack moves slowly across the sample as opposed to the
more usual instantaneous failure mode. Often stress-strain
curves do not start out with constant slope as shown in Fig. 3,
but instead have an initial curvature caused by takeup of
slack. The initial curved portion is called a "toe," and toe
compensation is described in ASTM D 638M and in ASTM D
882. Some stress-strain curves have no linear (i.e., no
Hookean) region from which to calculate the slope for modu-
lus values. In such instances the "toe corrected" origin and
another point on the curve are joined by a straight line. The
slope of the line is reported as the "secant modulus." The
elongation percentage at the second point selected is always
reported along with the value of secant modulus. Graphical
illustrations of secant modulus determinations are given in
ASTM D 638M and in ASTM D 882. Among the various test
methods, D 638M contains the most complete list of defini-
tions and symbols.
Determination of "tensile energy to break" is described in
ASTM D 882. The area under the stress-strain curve, e.g., see
Fig. 3, is divided by sample volume to obtain this quantity,
which has also been called "work-to-break" or "toughness"
[5]. Recommended units are megajoules per cubic meter.
ASTM D 882 describes how an integrated chart paper area
(distance 2) can be converted to energy/volume by using the
ordinate setting (force/distance of chart paper), the abscissa
setting (distance of elongation/distance of chart paper), and
the sample dimensions. Now that computers are used to
control operation and to treat data for SSA [32], numerical
integration is nearly instantaneous, and tensile energy to
break is likely to be reported more often. This SSA property
may prove to be useful for correlations with paint test results.
Interpretation of Stress-Strain Curves
Schematic stress-strain curves for various types of poly-
meric materials are shown in Fig. 6 [2]. This extremely wide
range of property variation is represented in coatings of vari-
ous types. Scales on the graphs give an order-of-magnitude
indication of property values. Brittle materials (6A) have high
543
~ooo
(/)
f__=
i q) I
1o O(~ 100
STRAIN (%) STRAIN (%)
2,ooo
03
I
500
STRAIN (%)
FIG. 6-General kinds of stress-strain curves for various
types of coatings. Scales indicate order-of-magnitude val-
ues.
modulus values (initial slope), tensile strengths up to about
8000 psi (5.5 x 107 Pa = 5.5 x 108 dynes/cm2), and elonga-
tions below 10%. Ductile materials (6B) usually have lower
initial slopes, tensile strengths in the 4000 to 6000 psi range,
and elongations of about 100%. The upper plot in 6B corre-
sponds to yielding with uniform sample deformation be-
tween the grips. The lower plot in 6B corresponds to a ductile
sample that necks down at the yield point, and further elon-
gation ( - 4 0 % to 110% in Fig. 6) occurs with increase in
length of the necked part of the sample. Elastomeric (rub-
bery) samples (6C) have much lower initial slopes than brittle
materials, tensile strengths of about 2000 psi, and elonga-
tions of the order of 400 to 500%. The upward curvature near
the end of the lower plot in Part C is attributed to strain-
induced crystallization [2].
Materials represented in 6A and 6B of Fig. 6 have Tg values
above the test temperature. Therefore, modulus values de-
pend on secondary interactions of polymer chain segments
and partial crystallinity, if any exists. The elastomeric mate-
rial (6C) has Tg well below the test temperature. Therefore,
modulus values depend in part on cross-link density, chain
entanglements, or both.
Stress-strain curves are carried out at a constant rate of
strain and results depend on strain rate selected. In genera], a
higher rate results in higher modulus. The two curves in 6A
could represent the same material strained at different rates.
In fact a large increase in strain rate could cause the plots of
6B to be converted to the plots of 6A. Dependence on strain
rate is evidence of viscoelasticity. Strain rate dependence in
SSA, therefore, has the same origin as dependence on oscil-
latory frequency in DMA (see Table 2).
544 PAINT AND COATING TESTING MANUAL
A recent study of silicone-epoxy resins cross-linked with
amines of various functionality [32] illustrates the extreme
range of stress-strain properties exhibited by coating films.
Tensile strength ranged from 31 to 4418 psi. Percent elonga-
tion ranged from 7 to 177%. Unfortunately, neither modulus
values nor tensile energy to break were reported. Property
variations were attributed to differences in degree of entan-
glement and to partial phase separation. In a network-form-
ing thermoset system, it would be impossible to get a tensile
strength as low as 31 psi unless incompatibility had pre-
vented occurrence of the network-forming reaction.
Examples of all types of behavior shown in Fig. 6 are repre-
sented in a single figure for coatings used on naval aircraft
[33] (see Fig. 4, Ref 33). One plot shows results for a polysul-
fide sealant that has a tensile strength of about 250 psi and an
elongation > 130%. Results for a flexible polyurethane primer
are a tensile strength of 3500 psi, a yield strength of 3200 psi,
an elongation at break of 90%, and an elongation at yield of
40%. The plot shows that a polyurethane topcoat yields and
breaks at about the same point: 4000 psi and 22% elongation.
The plot for an epoxy primer shows brittle behavior (no yield
point), a tensile strength of 2300 psi, and an elongation at
break of 7%. The authors [33] report that replacing the epoxy
primer by the flexible polyurethane primer eliminated the
need for the sealant coat.
SSA has been used extensively to characterize cationic UV-
cured cycloaliphatic epoxy/polyol coatings [34-36]. The
mechanism of introduction of polyol is a chain transfer step
[34], which permits use of a wide range of epoxy:polyol ratio
without need for stoichiometric balance. Selection of flexible
polyols with this wide formulating latitude permits prepara-
tion of cross-linked films with an extremely wide range of
mechanical properties. Numerous stress-strain curves have
been presented for this type of system with oligomeric pro-
pylene oxide polyols [35] and with oligomeric caprolactone
polyols [36]. Examples of stress-strain curves for a cycloali-
phatic diepoxide (CYRACURE | UVR-6110, Union Carbide)
and a propylene oxide triol (MW = 702) are shown in Fig. 7
[35]. The corresponding tensile properties are given in Table
3. Films from Compositions 1 through 4 all give brittle failure
(compare Fig. 6A) and only moderate changes in tensile prop-
erties (Table 3) despite a large change in composition. At
Composition 5 (70/30 epoxy:polyol, see Table 3) a yield point
is first noted, and thereafter very large property changes
occur despite relatively small changes in composition. Com-
positions in the 4 to 6 range (see Table 3) are reported to give
excellent post forrnability, as required for coatings on bever-
age can ends, while maintaining adequate hardness and sol-
vent resistance [34-36].
Relationship to Other Mechanical Properties
Stress-strain analysis (SSA) is used in a general way to
assess suitability of a binder for various coating end uses.
Most coating chemists associate modulus with coating hard-
ness and percentage elongation at break with coating flexibil-
ity. Quantitative correlations of these properties are not pub-
lished very often, however. The lack of published correlations
may result from the fact, noted above, that paint tests of
adherent coatings depend on coating-substrate interactions,
whereas SSA is carried out on free films. ASTM Test Method
Fief. No. 1 62.0
48.2
6
:E
5 34.5
4
3 20.7
6.9
~ 0
0 4 8 12 16 20 24 28
PercentElongation
FIG. 7-Stress-strain curves for UV-cured cycloaliphatic
epoxide films flexibilized with oligomeric propylene oxide
triol. Strain rate is 40% per minute. See Table 3 for tensile
properties.
for Elongation of Attached Organic Coatings with Conical
Mandrel Apparatus (D 522-88) describes how to calculate
percent elongation from the crack length in a conical man-
drel bend test. Comparison of elongation of adherent coat-
ings by the conical mandrel method and elongation of the
same coating as a free film from SSA would certainly be of
interest, but such comparisons were not found in the litera-
ture.
The logic of associating yield behavior in SSA with post
formability of coil coated metal was noted in 1977 [37]. In
1987, Koleske [35,36] confirmed that compositions that ex-
hibited a yield point performed well in the demanding post-
forming operations carried out on beverage can ends.
Evans and Fogel [38] provided convincing evidence that
gloss retention during abrasion of floor coatings is related to
the area under stress-strain curves. This area, divided by
sample volume, is called "work-to-break" or "toughness" as
noted in the subsection of this chapter entitled Definitions of
Tensile Properties. The authors provide a clear example of
the need to match strain rates when attempting to correlate
SSA results with paint test results.
Failure of attempts to correlate pencil hardness with pene-
tration hardness, e.g., Tukon Hardness, probably result be-
cause the former has a strong requirement for toughness,
whereas the latter is more dependent on the modulus value
at room temperature (see chapter subsection entitled
Relationship to Other Mechanical Properties).
DMA is much more generally applicable to determination
of cross-link density (see chapter subsection entitled
Determination of Cross-Link Density) than is SSA. If the Tg
of a coating binder is well below the temperature at which
 CHAPTER 46--DYNAMIC MECHANICAL AND TENSILE PROPERTIES 545

TABLE 3--Tensile propertiesa of UV-cured cycloaliphatic epoxide films flexibilized with oligomeric propylene
oxide triol.
C~176176162 Tensile Tensile
Film Epoxide, Triol, Modulus,d Strength, Elongation,
N o. b wt% wt% psi psi %
1 90.0 10.0 3.88 x 10s 9.5 x 10 3 6.6
2 85.0 15.0 3.72 X 10s 8.9 X 10 3 6.6
3 80.0 20.0 3.33 • 10s 8.4 x 10 3 7.4
4 75.0 25.0 2.95 x 10s 7.0 X 10 3 8.1
5 70.0 30.0 2.05 x 105 4.3 x 103 16.2
6 66.7 33.3 1.48 • 105 3.7 • 103 24.3
7 63.4 36.6 0.70 • 10s 2.5 x 103 54.0
8 60.0 40.0 0.26 X 105 2.0 x 103 88.4
~Strain rate, 40% per minute.
bKeyedto the plots in Fig. 7.
CWeight% of polymericbinder. (Filmsalso contain 2.9 wt% photoinitiator and 0.5 wt% flow agent.)
a1% secant modulus. (The modulus range expressed in pascals is 2.68 • 109,No. 1. to 1.79 • l0s, No. 8.)

SSA is carried out, t h e n the m o d u l u s from the initial slope of REFERENCES

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CONCLUSIONS
A wide range of a u t o m a t e d a n d computer-controlled in-
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f o r m u l a t i o n or changes in resin structure have had the de-
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