APPLICATION NOTES

Measuring and Understanding Tg (Glass Transition Temperature)

Arlon 2011

One of the first pieces of data anyone and inflexible (glass state) and in fact DSC defines the glass transition as
looks at when evaluating a potential the rubber band can be shattered. a change in the heat capacity as the
new material for Printed Wiring Upon standing and warming to room polymer matrix goes from the glass
Board (PWB) applications is its Glass temperature the rubber band will state to the rubber state. This is a
Transition Temperature (Tg). Over the again become flexible and rubbery second order endothermic transition
years we have all developed a set of (rubber like state). (requires heat to go through the
assumptions about Tg that affect transition) so in the DSC the
how we think about the design transition appears as a step
and manufacture of boards. Tg’s of transition and not a peak such as
materials used in our industry run might be seen with a melting
from 115˚C (for old-line difunctional transition.
FR-4) to about 250˚C (for high end
TMA defines the glass transition in
polyimide materials) with an almost
terms of the change in the coefficient
unbroken continuum in between
of thermal expansion (CTE) as the
based on various classes of resins,
polymer goes from glass to rubber
cross-linking agents and blending
state with the associated change in
ratios. We also have two primary
free molecular volume.
ways in which Tg is routinely being
measured: Differential Scanning Each of these techniques measures
Calorimetry (the “official” method), a different result of the change
and Thermo-Mechanical Analysis from glass to rubber. The DSC
(TMA). is measuring a heat flow effect,
whereas the TMA is measuring a
Glass Transition is a method
physical effect i.e the expansion in
to characterize a property of a
the two directions. Both techniques
polymeric material. The glass
assume that the effect happens over
transition is the temperature where
a narrow range of a few degrees in
the polymer goes from a hard, glass
temperature. If the glass transition is
like state to a rubber like state. The
very broad it may not be seen with
best way to envision this type of
either approach. This is similar in
transition is to put a rubber band
some ways to comparing inorganic
(rubber like state, very flexible) into
materials with thermoplastics in
a container of liquid nitrogen. When
terms of their melting points: many
removed the rubber band is solid
inorganic materials have sharp
melting points that take place within
a fraction of a degree of temperature, PTFE for instance has a minor • The higher the Tg the better will be
while most polymers have a much second order crystalline transition the long term thermal stability of a
wider melting range depending on the at about 19˚C that results in a minor material. (This unfortunately is not
distribution of their molecular weight. hiccup in the curve of dielectric necessarily true -- See “The Ups
and Downs of Continuous Operating
Since thermosetting (crosslinked) constant vs. temperature, but is
Temperature in the July 2001
resins such as the epoxies that are neither a melt point nor a real Glass
Newsletter.)
commonly used in our industry do Transition.
not have melting points, we look at The question of plated through
3. Most polymers have Tg’s but hole reliability and CTE(Z) is more
Tg as a measure of change of state,
technically its measurement complicated than being simply
but like their thermoplastic brethren,
depends on a crystalline transition a roughly linear function of Tg.
thermoset resins for a variety reasons That would be OK and works
so if a polymer is largely or totally
of do not all have sharp Tg transitions. out reasonably if you are always
amorphous in nature it may not
The DSC and TMA often give results have (or readily exhibit) a Tg. comparing PWB’s with the same
construction, fabric reinforcement and
that differ from one another by
The traditional wisdom concerning resin content, all of which contribute
5-10˚C when used to test a polymer.
Tg is that higher Tg’s confer several in some way to the CTE values.
Moreover, some polymers are more
distinct benefits in a resin system: And it is a mistake to equate thermal
amenable to DSC (epoxies for
instance) or to TMA (i.e. some of the • The higher the Tg, the lower stability with Tg because the two
the total amount of Z-direction involve totally different phenomena.
first generation polyimides such as
The most thermally stable epoxy we
Kerimid 601), because the transition is movement when a PWB is heated
ever used was in the old 1102 Burn-In
easier to observe using one technique (either in use or during process material that we sold for many years
over the other. For example if a steps such as solder reflow). This until operating temperatures started
polymer has a very large CTE above translates into reduced stress on making demands on it that were
the glass transition, the polymer plated through holes (PTH’s) during beyond its capability. Yet its Tg was
may be easier to test with the TMA processing, reduced risk of hidden only about 105˚C. Because it had very
than with the DSC, where the glass or intermittent PTH defects, and low levels of flame retardant it didn’t
transition may be almost invisible therefore better board reliability. have the tendency to decompose
when heated.
because it is very broad or does not • The higher the Tg the less likely
absorb an amount of heat easily it will be that rework will result in So What Do We Need Tg for?
detectable by the DSC. pads or lines detaching from the Firstly, it is a good check to make
surface of the PWB. This was a sure that your PWB’s are cured to the
Points to ponder: major reason for using polyimide on proper level. Using Tg as a guideline
1. DSC is the classic and “official” almost all military PWB’s for many will quickly detect severe undercure
way to determine Tg even though years where field repairs were often and allow a process to be tweaked to
in some cases there are polymeric important. (This is true!) ensure boards with good mechanical
materials that do not exhibit a sharp • The higher the Tg the less measling integrity.
Tg by DSC. (separation of resin from glass Secondly, it is a good first order
weave at the knuckles believed due indicator of resistance to process
2. Tg and Melt Point are distinctly to differential expansion of the glass temperatures. As you go to thicker
separate phenomena and even vs. the resin) will be experienced. and thicker boards (12 layer MLBs
when looking at thermoplastic (This is true!) and up) higher temperature resins do
materials such as are part of many provide improved measling resistance
laminates (PPO, PPE) their Tg’s and more reliability of PTH’s through
should not be construed as being thermal cycling. In addition if newer
melt points and vice-versa. lead-free solders do settle in at
higher temperatures than the current
systems, higher temp materials will
provide an added margin of safety.
Thirdly, there are applications in which
rework or repair temperatures may put
surface features (pads, lines) at risk,
and higher Tg materials do not soften
and “let go” of Copper foils as readily.
Fourth, Tg as measured by TMA
(DSC won’t do this) will give you an
actual value for Z direction expansion
both below and above the Tg
inflection point so that you can make
judgements as your boards get thicker
about the total amount of movement
you can expect and when to plan to
switch to a material with higher Tg
and therefore less movement.
The attached chart showing the
difference between a polyimide (Blue
Line — Arlon’s 35N) and a high Tg
Epoxy (Black Line — Arlon’s 45N)
shows how the point of inflection
makes a large difference in total Z
direction expansion between room
temperature and solder reflow
temperature (i.e. 250˚C even where
the rate of expansion below and
above the Tg’s is essentially the same.

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Ver 1.1 (Source: http://outgassing.nasa.gov )