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Home Coa ngs Proper es Glass Transi on Temperature: An Share

Important Thermal Property of Coa ngs

1. Resins and Coa ngs Proper es

2. Basics of Glass Transi on
Temperature
3. What Factors Govern Glass
Transi on Temperature of
Coa ngs?
4. Glass Transi on Temperature for
Specific Applica ons
5. Popular Methods to Measure
Glass Transi on Temperature

Resins are the most important components of paints and coa ngs. The resin type, chemistry
of the polymer chain, crosslinking, etc. have a key role in defining the final proper es
(physical, mechanical, thermal...) and performance of coa ngs.

Understanding some of the basic proper es of the polymers used in coa ngs is essen al for
the formulator while developing a high-performance product. Many of the basic proper es
of polymers are predictable based on their structural features i.e. linear, branched, rigid, or
flexible.

One such property of resins that holds key importance is “Glass Transi on Temperature”.
Each coa ng’s glass transi on temperature (Tg) is a net result of the effects of its

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cons tuents as well as the composi on and ra o of the resin used.

For any coa ng chemist, the glass transi on temperature is an important thermal property
of coa ngs which contributes to determining their applica on area and service life
proper es.

Let's review the basics of glass transi on temperature and the factors that govern it.

Glass Transi on Temperature, Tg, is defined as a temperature at which resin changes from a rigid glassy
material to a so material. It is not a mel ng point but involves the material becoming “so er”. This
temperature (measured in °C or °F) depends on the chemical structure of the resin and can therefore be used
to select the right resin depending upon the end-use of coa ngs.

Physically, the glass transi on temperature is the point at which polymer chains gain enough energy to
increase their mobility within the polymer matrix. The transi on from the glass to the rubber-like state is an
important feature of polymer behavior, marking a region of drama c changes in the physical proper es, such as
hardness and elas city of the coa ng.

The Tg is a very intricate concept and is not represented by a single value, even though it is an excellent star ng
point for understanding coa ng dynamics.

Free Volume Theory

The glass transi on temperature of a polymer can be understood in terms of the Free Volume Theory. The free
volume is a measure of the internal space available within a polymer matrix. When the free volume increases,
so do the freedom of movement of polymer chains.

A polymer chain that can move around easily will have an extremely low Tg, while one that doesn't move
so well will have a high one.
A polymer at Tg or below its Tg has no free volume for the polymer chains to move. Hea ng a polymer
above its Tg increases the free volume and makes the mobility of the polymer chains possible.

The free volume theory states that a consistent value of 2.5% free volume is required to achieve segmental
mo on.

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Free Volume Theory: Volume Changes in Polymers as Temperature Increases

(Source: Research Gate)

There are several factors that govern the glass transi on temperature of coa ng. It is impera ve to be aware of
these factors to find out how coa ngs perform in a given service condi ons and how Tg can vary with changes
in formula on, applica on, cure and crosslinking, and environmental parameters.

Type of Resin and Its Chemical Structure

The most common factors that determines Tg of coa ng is the resin use. Resins are broadly classified into three
groups – thermoplas cs, thermosets, and elastomers. They can be further divided into two types according to
their molecular arrangements i.e. amorphous and crystalline.

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Amorphous polymers have a random molecular structure that does not have a sharp mel ng point.
Instead, amorphous material so ens gradually as temperature rises. Amorphous polymers only exhibit a
Tg.
Crystalline or Semi-crystalline polymers have a highly ordered molecular structure. These do not so en
as the temperature rises but have a defined and narrow mel ng point. Crystalline polymers exhibit a Tm
(melt temperature) and typically a Tg since there is usually an amorphous por on as well (“semi”-
crystalline).

A Heat Versus Temperature Plot for a Crystalline Polymer (L) and Amorphous Polymer (R)
A Heat Versus Temperature Plot for a Crystalline Polymer (L) and Amorphous Polymer (R)
(Source: PSLC)

KEY FACTS

1. As crystallinity influences the Tg, it is important to differen ate

between amorphous and semi-crystalline polymers.
2. Many synthe c polymers used in coa ngs are amorphous
rather than crystalline, so they do not have a dis nct mel ng
point.

Thermosets and Thermoplas cs

Typical thermoset polymer will exhibit high Tg due to restricted molecular mobility driven by higher density
and higher quan ty of crosslinks (e.g. mul func onal epoxies). While thermoplas c polymer chains are capable
of a wider range of movement in terms of flow or transla onal mo on. But thermoplas cs with rigid
backbone structures tend to have higher Tg because of:

Bulky side groups that restrict/hinder rota on around the primary chain, and
Intermolecular interac ons

For example, linear alipha c amorphous polymers are more likely to have low Tg (such as high-density
polyethylene, Tg = -120 to -130°C), in contrast to polymers with more rigid backbone structures, e.g.,
poly(benzimidazole), with a Tg of ~ 490-500°C.

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Glass Transi on Temperature of Various Polymers

The chemical building blocks of a polymer, i.e., backbone, side chains, and chain-to-chain interac ons, and how
all the chemistry is connected plays a dis nc vely significant role in finding the glass transi on temperature.

To sum-up, following structural features of resin impact Tg:

In straight chain polymers, increase in molecular weight leads to decrease in chain end
Molecular Weight concentra on resul ng in decreases free volume at end group region and hence,
increases Tg.

Inser on of bulky, inflexible side group increases Tg of material due to decrease in

Molecular mobility. Also, changing monomer composi on varies Tg of the polymer. For example,
Structure & if the ra o of hard and so monomers has mostly the hard monomer, then the Tg of
Monomer the final polymer will be higher. In a styrene-butadiene latex emulsion, the styrene
Composi on has a Tg of ~100°C while that of butadiene is ~-85°C. Changing the ra o of styrene to
butadiene will change the Tg.

Crosslinking of a polymer changes many other characteris cs of a polymer.

Crosslinking reduces the mobility of polymer chains and decreases the free volume.
Chemical cross-
This reduc on in mobility shows in form of increased stress in a polymer on extension.
linking and
Coa ng Tg will increase as the crosslink reac on con nues. The higher the cross-linked
Modulus
density, the higher the Tg & the modulus. The build-up of coa ng Tg is also dependent
on the catalyst concentra on and cure temperature.

Presence of polar groups increases intermolecular forces; inter chain a rac on and
Polar groups
cohesion leading to decrease in free volume resul ng in increase in Tg.

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Other factors that have a significant impact on glass transi on temperature are:

Branching
Alkyl chain length
Bond interac on
Flexibility of polymer chain
Film thickness, etc.

When focused on coa ngs, we also need to consider the polymer’s interac ons with pigments, addi ves,
plas cizers, residual solvents, the substrate, and the influence of environmental condi ons.

Pigments and Extenders

Pigments and extenders are important

cons tuents of coa ngs and their physical
proper es play a key role in defining the
final proper es of coa ngs. Pigment
Volume Concentra on, PVC, indicates the
volumetric concentra on of extenders (or
pigments) in the coa ng.

CPVC (Cri cal Pigment Volume

Concentra on) stands for PVC
corresponding to the random ghtest
possible packing of the extender (or pigment) par cles and the minimum amount of binder necessary to fill the
inters ces between extender par cles. Pigment volume concentra on (PVC) influences mechanical behavior of
the coa ngs, thus influences glass transi on temperature of coa ngs.

Addi on of Plas cizers

Addi on of plas cizer increases the free volume in polymer structure. Plas cizers not only increase elas city
but also lower the glass transi on temperature, which adversely affects blocking stability and can lead to s cky
surfaces.

This results in polymer chains sliding past each other more easily. As a result, the polymer chains can move
around at lower temperatures resul ng in decrease in Tg of a polymer.

» Get Tips to Select the Right Plas cizer for Your Coa ngs Applica on!

Coalescing Agents

Coalescing agents func on as temporary plas cizers for the polymer par cle and thereby reduce the minimum
film forming temperature* (MFFT). The MFFT of the emulsion relates directly to the glass-transi on
temperature (Tg) of the polymer.

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The higher the Tg, the higher the MFFT.

Coalescing agents allow the forma on of polymeric films at ambient temperature condi ons of film applica on,
even of polymers showing a MFFT of above these temperature condi ons. Coalescing agents typically lowers Tg
of the polymer.

*The minimum film-forming temperature is the lowest temperature required to coalesce a polymer and applied
to a substrate into a thin film.

» Understand the Role of Coalescing Agents in Coa ng’s Film Forma on!

Water or Moisture Content

Increase in moisture content leads forma on of hydrogen bonds with polymeric chains increasing the distance
between polymeric chains. And, hence increases the free volume and decreases Tg.

Effect of Entropy and Enthalpy

The value of entropy for amorphous material is higher and low for crystalline material. If value of entropy is
high, then value of Tg is also high.

Pressure and Free Volume

Increase in pressure of surrounding leads to decrease in free volume and ul mately high Tg. Overall, it is the
resin’s structure, molecular weight, crosslinking, func onal groups, interac on with other components of the
formula on and applica on condi ons, all have direct impact on glass transi on temperature.

It is also important to note that Tg is an important property while studying viscosity at a given temperature,
physical and chemical proper es of the coa ng formula on.

Now we are aware that understanding the glass transi on temperature can be cri cal for determining coa ng
suitability for specific applica ons. Tg is an especially important considera on in the selec on of the proper
resin for a for desired coa ng performance.

Here are the few examples (not an exhaus ve list yet) explaining:

Strategies to Achieve High Tg End Applica on Requirements

Compared to conven onal coa ngs, the UV variants The corrosion coa ng must have a glass transi on
are comprised of lower molecular weight materials temperature, Tg, above the opera ng temperature of
that react to make denser, highly cross-linked the pipeline to prevent damage from pipe
networks. They also o en have higher Tg and make movement.
harder films with good abrasion and chemical

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resistance.

Mul func onal epoxy resins have commonly been Industrial paints and coa ngs need a higher Tg
used to produce highly crosslinked coa ngs with high because high hardness and the lack of tack are
glass transi on temperatures. The Tg of an epoxy is requirements at the service temperatures, meaning
affected not only by the choice of epoxy, curing the coa ng will be more rigid and less suscep ble to
agent and filler used, but also by the curing dirt pick-up.
condi ons. Epoxies demonstrate a wide range of Tg,
from as low as 50°C to upwards of 250°C. In addi on
to improving its performance proper es, adding heat
while curing the epoxy helps improve its glass
transi on temperature (Tg).

Acrylonitrile-butadiene rubber toughened vinyl Glass transi on temperature has direct impact on
ester resins have been found to produce high glass the hardness and flexibility of the coa ng. For
transi on temperature thermose ng materials. example, a coa ng technology used for making floor
Vinyl ester precursors ranging in number average polish or house paint would both make extremely
molecular weight from 3600 to 3800 have been poor choices for an elastomeric roof coa ng. Thus, Tg
made into toughened coa ngs having glass transi on is an important property to consider while selec ng
temperatures a few degrees above 140°C. resin for a given applica on.

Another approach to making high temperature

polymeric resins for protec ve coa ngs is to gra
amino groups on polyetherimides. Coa ngs with
glass transi on temperatures ranging from 150 to
210°C were produced by this method.

Polycyanurates, as products of a cyclotrimeriza on

reac on of cyanate ester monomers, are another
route to high glass transi on temperatures.

Several methods are available to measure glass transi on temperature that typically provide a range of values
with subtle to significant differences. These test methods include:

1. Differen al Scanning Calorimetry (DSC)

2. Differen al thermal analysis (DTA)
3. Dynamic mechanical analysis (DMA)
4. Thermo mechanical analysis
5. Thermal expansion measurement
6. Micro-heat-transfer measurement
7. Isothermal compressibility
8. Heat capacity determina on, etc.

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Among these methods, DSC, DTA and DMA are by far the most dominant techniques used for glass transi on
temperature measurements.

Let’s discuss these techniques in detail...

Differen al Scanning Calorimetry (DSC)

Differen al Scanning Calorimetry (DSC) is a thermo-analy cal technique used to study the thermal proper es
of the polymer using a differen al scanning calorimeter. It is widely used to determine the glass transi on
temperatures of resins. This test method applies to amorphous materials or to par ally crystalline materials
containing amorphous regions, that are stable and do not undergo decomposi on or sublima on in the glass
transi on region.

In this method, a differen al scanning calorimeter measures the difference in heat flow to a sample and to a
reference against me or temperature while the temperature change of the sample, in a specified
atmosphere, is programmed.

Glass Transi on Temp. Measurements of Different Polymers Using DSC

(Source: Me ler-Toledo Analy cal)

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The test standards used to find Glass Transi on Temperature of resins via DSC include:

ASTM E1356-08 (2014) – Standard Test Method for Assignment of the Glass Transi on Temperatures by
Differen al Scanning Calorimetry
ISO 16805:2003 – Binders for paints and varnishes — Determina on of glass transi on temperature
ASTM D3418-15 – Standard Test Method for Transi on Temperatures and Enthalpies of Fusion and
Crystalliza on of Polymers by Differen al Scanning Calorimetry
ASTM D6604-00(2017) – Standard Prac ce for Glass Transi on Temperatures of Hydrocarbon Resins by
Differen al Scanning Calorimetry
ISO 11357-1:2016 – Plas cs — Differen al scanning calorimetry (DSC)
Part 1: General principles
Part 2: Determina on of glass transi on temperature and step height

Differen al Thermal Analysis (DTA)

Differen al Thermal Analysis (DTA) is a popular thermal analysis technique and is o en employed for
measuring Tg of the material. In principle, differen al thermal analysis is a technique which is similar to
differen al scanning calorimetry (DSC).

The technique involves an inert reference material.

The material being studied in DTA undergoes various hea ng and cooling (thermal) cycles where the
temperature difference between the reference and the material under analysis is determined.
Both the reference and sample materials are kept at the same temperatures throughout the hea ng
cycles to ensure that the tes ng environment is uniform.

Measurement Principles of DTA

Measurement Principles of DTA (Source: Hitachi High-Tech Corpora on)
Where Graph (a) Shows the Temperature Change of the Furnace, Reference and Sample Against Time
Graph (b) Shows the Temperature Difference (ΔT) Against Time Detected with the Differen al Thermocouple

The test standards used to determine Glass Transi on Temperature of resins via DTA include:

ASTM E794 - 06(2018) – Standard Test Method for Mel ng and Crystalliza on Temperatures by Thermal
Analysis

Dynamic Mechanical Analysis (DMA)

Dynamic Mechanical Analyzer measures the s ffness of materials as a func on of temperature, humidity,
dissolu on media or frequency.

Typical DMA Analysis Graph

Typical DMA Analysis Graph

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In this technique, a mechanical stress is applied to the sample and the resultant strain is measured by the
instrument. These parameters are used to evaluate glass transi ons, degree of crystallinity and s ffness
behavior of the sample.

When dealing with films and coa ngs, DMA is applied in 3 different op ons:

Applica on of DMA
Applica on of DMA

The test standards used to determine Glass Transi on Temperature of resins via DMA include:

ASTM E1640 - 13 – Standard Test Method for Assignment of the Glass Transi on Temperature by Dynamic
Mechanical Analysis

Note: It is impera ve to understand when, how, and why coa ngs perform as they do from varying applica on
methods, differing cure profiles, and a wide array of environmental condi ons.

Get Inspired: DMA Prac cal Interpreta on with Case studies for Polymer Development

3 Comments on "Glass Transi on Temperature: An Important Thermal Property of Coa ngs"

Johnson C Mar 23, 2022
Good
Jordi F Nov 15, 2020
Great ar cle for those of us who barely knows about Tg & MFFT although we would like to learn
more about DSC technics and how modifica ons on coa ngs formula on could affect directly to Tg
proper es
Peter G Nov 4, 2020
Very nice ar cle for those of us who are just learning about coa ng formula on and failure analysis.

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