E1 Determination of the molecular weight via vapour pressure osmosis

E1: Determination of the molecular weight via

vapour pressure osmosis

Task

Determine the average molar mass of a polyethylene glycol via vapour pressure osmosis
at aqueous solutions by using an already created calibration.

1. Basics

The basic for the determination of the molecular weight through vapour pressure osmosis is
the Raoult´s law:

/ = 1- (1)
P: vapour pressure
Index 1: solvent
Index 2: solute
*: pure solvent
: mole fraction of the solute

For the chemical potential of the solvent you get

= + RT ln { / } (2)

When you solve a specified amount of molecules in pure solvent then the mole fraction of the
solvent changes from = 1 to = 1 – . The vapour pressure of the solvent undergoes a
decline of ΔP = - . Exists a highly diluted solution also after the dissolving process, so in
the first approximation the Raoult´s law can be applied and the change of the chemical
potential Δ of the solvent at the dissolving process is [with the equations (1) and (2)]

Δ = - = RT ln {1 – } (3)

At the vapour pressure osmosis the change of the vapour pressure isn´t measured directly but
one in the solution also adjusting increase of temperature ΔT.

How is this increase of temperature achieved?

The polymer solution is only via the gaseous phase of pure solvent in contact with the pure
liquid solvent. The chemical potential of the solvent in the solution is lower than in the
gaseous phase and in the pure solvent. Therefore solvent molecules condense more on the
solution because so they can decrease their chemical potential or

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 Determination of the molecular weight via vapour pressure osmosis

alternative interpreted because the vapour pressure over the solution is smaller than over the
pure solvent. The solvent molecules are delivered in addition from the big stock with the pure
solvent in the gaseous phase. Consequently in the solution condensation heat is released and in
the pure solvent heat of evaporation is consumed. The solution warms up and the pure solvent
cools down. With increasing temperature the vapour pressure of the solvent increases at the
solution side whereas it decreases at the pure solvent side. These effects lead to a steady state
with constant temperature difference between solution and pure solvent. A huge surplus of
pure solvent and a big steam area in comparison to the solution amount achieve that the effect
of cooling the pure solvent plays no role and that during the measurement the vapour pressure
equilibrium between pure solvent and steam area survives.

The temperature difference ΔT is proportional to the difference of the chemical potential from
the solvent in both liquid phases.

Δ ~ - ΔT (4)

With equation (3) you get

RT ln{1 – } ~ - ΔT (5)

You can rearrange equation (5) under the assumption of a very small mole fraction for

/ M~ ~ ΔT (6)

: molar mass of the solvent :

density of the solvent
M: molar mass of the solute
: concentration of the solute [g/l]

The increase of temperature ΔT is experimentally easily accessible and is clearly connected via
equation (6) with the wanted molar mass of the solute. Indeed for the evaluation of the
measuring results the following modification of equation (6) is more suitable

ΔT ~ K /M (7)

In equation (7) K is a constant of the device that has to be determined by calibration with the
help of a calibration substance of known molar mass.

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 Determination of the molecular weight via vapour pressure osmosis

Two aspects should be particularly highlighted

1. At molecular mass distributions the value of the molar mass is equivalent to the number
average

2. Already diluted solutions show deviations from the ideal behaviour which can be
adapted by a virial series whereby and are equivalent to the second and the third virial
coefficient.

ΔT = K (1/M) + + + ... (8)

To get the first virial coefficient K/ and with it the molecular weight you have to determine
the boundary value of the reduced temperature increase ΔT/ for infinite dilution by
extrapolation from a range of measured data.

2. The vapour pressure osmometer OSMOMAT 070

The OSMOMAT 070 is suitable for the determination of the average molecular weight of
polymers in aqueous and organic solvents. For this the substances should be in the
concentration range of 1x10-3 to 50x10-3 mol/kg. To be measured substances have to be
completely dissolvable in a suitable solvent and must not dissociate or undergo chemical
interactions with the solvent. The measurements can be done in the temperature range of 30°C
to 130°C. A molecular weight of 50 to about 50.000 Dalton in organic solvents and to about
5000 g/mol in water can be determined. Of each to be measured substance at least three
solutions with graded concentration have to be measured. The calibration is made with
solutions of known molality respectively osmolality. The vapour pressure osmometer
OSMOMAT 070 is also suitable for the determination of the total osmolality of aqueous
solutions.

2.1 The measuring method

Two thermistors, which are connected in differential measurement as temperature sensors, are
arranged hanging in a thermostated measuring cell. The temperature sensors, which at first are
encased with solvent drops, adjust to the cell temperature so that there is no temperature
difference between them. After replacing one of the solvent drops by a solution drop it comes
to condensation of solvent vapour over the solution drop due to the lower solvent vapour
pressure. The resulting condensation heat leads to a measurable increase of temperature
at the solution drop. The

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 Determination of the molecular weight via vapour pressure osmosis

resulting temperature difference between both temperature sensors, which are a part of a
Wheatstone bridge with a resolution of 5x10-5 °C, is transformed in a direct current voltage
signal. The measured value is proportional to the osmolal concentration of the solution but can
be influenced by heat losses. Therefore a calibration of the measuring system with solutions of
known molality and osmolality is necessary. Because the osmotic pressure of polymer
solutions depending on the concentration isn´t linear at least three solutions with graded
concentration of to be measured substances will be measured. A final statistical calculation of
the measurement results by a linear regression calculation eliminates the non-linear behaviour.

2.2 Device description

2.2.1 The measuring system

The whole measuring system consists of the cell unit “OSMOMAT 070” and a control unit.
The cell unit contains the in the measuring cell hanging measuring probes including bridge
amplifier as well as all electronic components for the thermostatic control while the power
supply, control and measurement indication respectively evaluation takes place in the control
unit. The control unit SA has a monitor and a keyboard. It guides the user by use of software
through the measurement, displays the data graphically, calculates the molecular weight and
can print the measurement result with linear regression and the graphics. There is a help file
for the control unit SA.

2.2.2 The cell unit

On the left there are two LEDs at the front of the OSMOMAT 070 (figure 2-1), “power” (1)
for displaying the mains voltage supply and “ready” (2) for displaying the temperature status.
This LED lights red during the heating up phase when the measuring cell not yet achieved the
given set point and changes to green when the set point of temperature is adjusted. By
pressing the light button (3) at the right front a LED that illuminates the internal space is
turned on for approximately 25s. The dropping of the solution respectively the solvent with
the help of syringes can be observed visual via a mirror (4) which is also found at the front.

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 Determination of the molecular weight via vapour pressure osmosis

Figure 2-1: OSMOMAT 070 front

2.2.3 Setup of the measuring cell

The measuring cell is located in a thermostat with very constant temperature which can be
adjusted between 30°C and 130°C in 1°C steps. The cell is equipped with a cylindrical beaker
in which a small amount of solvent is situated (fill level circa 1 cm). Steam wicks in the shape
of filter paper strips stand in the beaker to achieve 100% steam saturation. Two measuring
probes with temperature sensor hang in the solvent vapour saturated cell room. The lower
ends of the measuring probes will be encased with solvent drops and solution drops. A
consistent droplet size will be achieved by wire spirals which are located at the lower end of
the measuring probes. They simplify the purging of the probes because the liquid can run off
helical and the probe will be wetted all around. The feeding of solvents and solutions is made
by glass syringes which are positioned in the head of the cell together with the measuring
probes.

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 Determination of the molecular weight via vapour pressure osmosis

13- syringe for dropping the solvent 22-pivoted mirror

14- syringe for dropping the solution
15- measuring probe in position A for
solvent
16- measuring probe in position B for
sample solution
17- measuring channel for external
review of the head temperature
18- steam wicks
19- heat insulation filter
20- solvent
21- window for observing the droplet size
at the measuring probes
23-cell lid
24-cell head with separate
thermostatic control
25-measuring channel for external
review of the cell temperature
26-beaker
27-cell room with saturated solvent
vapour
28-cell block with heating coil and
temperature sensor for thermostatic
control

Figure 2-2: OSMOMAT 070 measuring cell

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 Determination of the molecular weight via vapour pressure osmosis

2.2.4 The cell head

The cell head has an own temperature control which automatically adjusts to the cell
temperature. It closes the measuring cell at the top end and ensures the preheating of the
syringes. A temperature fine adjustment for optimisation of the temperature difference
between cell and cell head is possible via a potentiometer ant the back side. The temperature
of the cell heads should be approximately 0,5°C lower than the cell temperature. For
avoidance of temperature influences the cell head is covered with a lid that is fixed with a
knurled screw.

29- Teflon lip seal for sealing the cell room

30- guide tube for alignment of the syringe cannulas to drop point of the measuring probes

Figure 2-3: OSMOMAT 070 cell head

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 Determination of the molecular weight via vapour pressure osmosis

31- threaded bolt for screwing the cell head (screw on manually) 32-
position A of the reference measuring probe
33- position B of the measuring probe
34- syrringe position 0 solvent for reference measuring probe 35-
syrringe position 0 solvent for baseline
36-syrringe position 1 lowest concentration of the sample
37-syrringe position 2 next higher concentration of the sample 38-
syrringe position 3 next higher concentration of the sample 39-
syrringe position 4 highest concentration of the sample
40-knurled screw for fixing the cell lid

Figure 2-4: OSMOMAT 070 cell head/lid top view

3. Hints for the implementation of a measurement

The calibration of the measuring system with the determination of the cell constant is done
with aqueous KCl solutions of different concentration in the area between 4 and 24
mmol/kg. For the determination of the molar mass of the sample solutions of the polymers in
the same (molar) concentration range as at the calibration are required. An approximate
knowledge of the measured molar masses is therefore necessary.

The bottom of the measuring cell is covered with a layer of pure solvent. After a sufficient
long tempering time (at least 2 hours) a constant saturated solvent atmosphere in the steam
room sets in. This process is accelerated by the usage of steam wicks from filter paper.

The measured value recording and the evaluation are made automatically by the computer
programme.

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 Determination of the molecular weight via vapour pressure osmosis

The only but huge problem is the manually application of the drops (solvent, sample solution)
at the measuring sensors:
The dripping and rinsing of the solvents and solutions has to be done very conscientious and in
a consistent temporally cycle.

Before each rinsing process the button “light” at the front of the device is pressed to turn on
the interior light for approximately 20 seconds and to observe the dripping via the mirror.
Because measuring effects are measured with a temperature resolution of circa 1x10 -5°C each
temperature fault has to be reduced to a minimum. For a reproducible measurement the size of
the drop which encloses the end of the probe has a huge relevance. For producing an optimal
reproducible drop size and an efficient rinsing of the temperature sensors the handling takes
place in the following way:
The syringe is pushed down to the limit when rinsing so that the end of the cannula stands over
the probe spiral. The liquid is applied at the probe spiral through sensitive pushing down and
simultaneous slight rotation of the syringe piston. The temperature sensor is surrounded and
wetted with liquid. After two to three drops are dripped off the flow is stopped at the moment
in which a drop is dropped. Due to the continued flow of the liquid a medium drop gets caught
surrounding the temperature sensor. The syringe is released careful and goes back to the initial
position.

The reproducibility of the measurement depends crucially on the regularity of the drop size.

Figure 3-1: Rinsing the probes

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 Determination of the molecular weight via vapour pressure osmosis

The complete rinsing process should be done always after the same rite. First the right
measuring probe is rinsed with two to three drops then the left reference probe is rinsed with
one drop and then again the right measuring probe is rinsed with two to three drops. At repeat
measurements with the same concentration only one new drop is carried to the measuring and
reference probe. After applying the drops the “start” button is clicked and therewith the
sampling time is started.
Because the software does not permit subsequent corrections in the measuring cycle it makes
sense to drive the first measurement as a “sample” to learn the technique, then to stop and then
start the second “actual” measuring run. A few sample trials for applying the drops on the
thermistors are in any case necessary.

4. Instruction sheet

The vapour pressure osmometer is at the beginning of the test already prepared for the
measurement:

- tempering on 50°C and saturation of the gaseous room with water vapour are already
ensued

4.1 Making the sample solutions

A concentrated stock solution (48 g/kg) is provided from the PEG to you. First you have to
create a serial dilution from this stock solution:
Polymer solution and water are dosed into sample glass with the help of disposable syringes
and the required masses are ascertained by weighing (analytical balance).

Calculate first the masses of stock solution and water which are necessary for production of 10
g diluted polymer solution of the stated concentrations:

concentration PEG mass stock solution mass water

48 g/kg 10 g 0

32 g/kg

16 g/kg

8 g/kg

0 0 10 g

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 Determination of the molecular weight via vapour pressure osmosis

4.2 Preparation of the dosing syringes

The glass syringes will be filled completely (0,9 ml) with the diluted solutions. No air bubbles
are allowed!
The filled syringes will be placed in the order of increasing concentration at the positions 1 to
4 in the measuring head. Two syringes filled with pure solvent are placed at the both with “0”
denoted positions.
The filled syringes have to be tempered at least 30 minutes in the measuring head before
starting the measurement.

4.3 Preparation of the software

The sample designation and the accurate concentrations of the sample solutions are filled in
the prepared table. With “start” ensues the beginning of the pre-programmed measurement
routine.

4.4 Determination of the base value

First the value of the base line has to be ascertained:

Measuring and reference probe are rinsed with several drops of solvent and are equipped with
a drop*. The programme point “base line adjustment” is already marked. With “start” begins
the measured value recording, after 5 minutes the measurement ends.
The measurement of the base value is repeated two times.

*To obtain reproducible results the following procedure has been proven:

- Turn on the measurement chamber lighting (It goes out again after 20
seconds!)
- Grab the syringe at the top between your thumb and middle finger
- Push down carefully until it stops
- Press the piston carefully and slowly with the forefinger
- Observe the drop at the probe through the mirror
- Interrupt dosage immediately after a drop falls from the probe

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 Determination of the molecular weight via vapour pressure osmosis

4.5 Measurement of the sample solutions

The measurement of the sample solutions ensued analogue:

The corresponding sample solution is chosen in the programme menu (“select”). Afterwards a
new drop solvent is applied at the reference probe and a drop sample solution is applied at the
measuring probe according to the procedure described above and the measured value recording
is started. The measurement is repeated for each sample solution 3 times (this means 4
measurements!). When changing the sample solution the measuring probe has to be rinsed first
with approximately 8-10 drops of the new solution. At repetition measurements the application
of a new drop on measuring and reference probe is enough.

4.6 Base line correction

After measuring the last sample solution the programme point “base line correction” is
chosen (“select”). After rinsing the measuring probe with solvent the base value is measured
again (several times) analogue 4.4.

4.7 Evaluation

The evaluation is done automatically on the basis of an already saved calibration of the
measuring system.
After the renewed measurement of the base value (4.6) all items on the programme should
have a green tick. With “finish” you get to the evaluation.
In a table all measuring values, the average values for each concentration of the sample
solution and the resulting values for the average molar mass of the sample are displayed.
Because the essential source of error at this experiment is the untrained operator rarely occur
systematic but for it individual random measuring errors. A considerable improvement of the
overall result can be achieved by the removal of obviously outliers in the measuring values.
Individual measuring values with equal sample concentrations which differ obvious from the
respective average value should be deactivated in the measuring value table.
With the option “linear regression” the average values for the different concentrations are
averaged and the final measuring value is ascertained by extrapolation on concentration “0”. If
there is an obvious deviation of the average value from the regression line for one sample
concentration it is absolutely useful also not to consider this value for the calculation.
If the base values differ before and after the sample measurement significantly from each other
(difference more than 3) then you should not use the option “drift correction” because the
reason for this deviation is for sure insufficient rinsing of the measuring probe.

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After finishing the evaluation you have with the option “print analysis” the opportunity to print
a report of the measuring result.

5. Control questions

1. Base of the measuring effect at vapour pressure osmosis is a colligative property. What is
meant by colligative properties? Name more measuring methods whose principle is based on
colligative properties!
2. Explain the differences between mass concentration, volume concentration, molarity and
molality!
3. Name advantages and disadvantages of concentration information in relation to the
volume respectively the mass!

Protocol:
The Protocol contains
- Brief summary of the theory of Vapor Pressure Osmosis
- Description of the observations
- Self-calculated graph based on the response results and comparison
with the output of the software
- Error discussion

E2: Determination of styrene in

polystyrene (HS-GC/MS)

Determination of styrene (residual monomer content) in PS yoghurt cups via headspace

- gas chromatography with a mass selective detector

Method

chromatography belongs to the method family in which a mixture has to be separated in its
components by using a mobile phase carrying the mixture through a stationary phase over a
certain separation column. In doing so there are complicated and depending on numerous
parameters interactions of adsorptive and distributive nature between the separated
components and the stationary phase. When the parameters are optimized appropriate the
separating task, the components leave chronological one after the other the separation column
at the end (you get a so called outer chromatogram). In the gas chromatography, named after
the nature of the mobile phase, you are working either with so called packed columns or today
in analytical applications in normal case with capillary columns. In the packed columns the
stationary phase consists of a solid, in the capillary columns it is usually worked with an at the
capillary wall adhesive liquid. A gas which suits to the detector is used as a mobile phase.
When using a heat conductivity detector e.g. hydrogen is used as a carrier gas.
An optimization of the gas chromatographic separation process ensued generally through
choice of separating liquid (at capillary columns the coverage of the inner column wall),
variation of the flow of the carrier gas , choice respectively modification of the detector
and through a temperature programmed mode of operation.

The headspace technique which should be used in this test is especially suitable for highly
volatile analytes in solid or liquid matrix. The sample is filled in a small bottle which is then
sealed mechanically tight. The flask can now be heated in a thermostat (machine, oven)
whereby an equilibrium between the analyte in the liquid respectively solid sample and the
gaseous phase
(the vapour space above) is adjusted. Now the removal of a partial volume of this gaseous
phase occurs automatically. This partial volume is transferred via a temperate syringe in the
column.

In statically headspace analysis the signal is proportionate to the partial pressure of the analyte
above the sample. We are using a mass selective detector with the measurement techniques
SCAN and SIM (Selected Ion Monitoring) for the determination of styrene. In the SCAN
technique a total ion current chromatogram (TIC) of the sample is recorded whose peaks can be
identified with the help of their spectra by library comparison. In contrast the SIM
technique uses selected significant masses of the substance spectra and records their mass
chromatograms. These are also used based on the data retention time, mass number and the
rate of mass number to intensity for the identification of substances as well as the quantification.

The calibration occurs after the process of the method of adding. The to be calibrated
substance is added in form of a solution to the sample in the headspace glass. In contrast to
the method of adding for liquid samples the addition occurs in this case to the gaseous phase.
Therefore this process can also be called gaseous phase addition method. If now sample and
sample with addition are analysed two data for the particular area totals result, which are
charged exactly like as for the method of adding for liquid samples.

Equipment and chemicals

Equipment

- GC/MS Trace GC (Thermo Finnigan) with autosampler Combi PAL

- carrier gas: pure helium (so called 5.0 He)
- capillary separation column HP 5 (l = 30 m; i.d. = 0,32 mm)
- detector DSQ: mass selective detector ( a kind of quadrupole mass spectrometer)
- analytical balance
- headspace flasks, 22 ml volume, seals and caps

Chemicals and standards

- styrene
- hexane as solving agent

Samples and sample preparation

Standard
Fill in a 5 ml graduated flask some hexane and determine the mass of the closed flask. Then
add 25 µl of styrene with a micro syringe and determine the increase in weight. Fill now with
hexane to the calibration mark.

Analysis samples
Grind a provided cup of polystyrene with a scissors for the analysis. Now weigh 150 mg of
the hackled polystyrene sample in each of the three headspace vessels (vials).
- Lock the first vial with a seal and a magnetic screw cap.
- Add 1 µl of the styrene standard to the second vial and lock it.
- Add 2 µl of the styrene standard to the third vial and lock it.

Execution of the measurements

Preparation of the measuring system

- Turn on the monitor and the printer. The computer, the GCD and the HS-sampler are
already in an operating state and will not be turned off. The control of the HS-sampler
occurs directly via the panel (Combi Pal) at the device.
 The supervisor will explain you the functional principle!
- Station the first vial with 150 mg polystyrene in the first position of the HS-
autosampler (Tray2)
- On position two and three of the HS-autosampler follow both prepared measuring
samples.

Measuring program

- Start the software <XCalibur> with a double click. At the monitor the Home Page
appears (compare figure 3.4-1).

Figure 1: Home Page

- Open push button [Instrument Setup]

- File/Open
- Choose the following method: confirm `Polystyren_HS` with `open`
The content of the method can be checked via the individual push
buttons `DSQ` and `Trace GC`.
- Close Instrument Setup (without changes)!
- Open push button [Sequence Setup]
- File/New
- new window appears: New Sequence Template
- insert the following entries:

General

- Base File Name: insert e.g. CUT05 + date (yymmdd)

- Path: click Browse and select
C:/Xcalibur/Data/CUT0#
- Instrument method: click Browse and select
`Polystyren_HS`
- Starting Number: 1

Samples

- Number of Samples: 3
- Injection per Sample: 1
 - Initial Vial Position: 1

Bracket Type

- click open
- confirm window with <OK>
- A new window appears in which the entries can be checked and
changed.
- insert injection volume: 1 µl
Hint: If you want to change the content of the individual cells, you have
to click in the cell and edit with the key [F2]!

Switch to autosampler (Combi Pal)

- adjust autosampler (change via control knob; with turn, push and confirm of the
middle knob)
- choose Tray: Tray 2
- first (1. sample position): 1
- last (last sample position): 3
- increment: 1
- count: 1
- method: `Styren`
- push key Home [F4] and
- finish entry with key Start

[F4] Switch to PC software

- Sequence Setup still open

- under Actions/Run Sequence
- new window: Run Sequence
Attention: Tick at the following attitudes:
- Start When Ready P
- Pre Acquisition P
- Post Acquisition P
- After Sequence Set System:
ON Attention: Other ticks are not
allowed!
- User: e.g. insert group
- close window with <OK>

Data evaluation

- Retrieve the data evaluation via the menu bar [View/Roadmap View].
- Open the appropriate data file via Qual
Browser File/Open/PMS##/`name`
- under menu bar: Actions/Peak Detection/Toggle click on `Detection` in `All Plots`
and note all area values
You can calculate the amount of styrene in the sample from the area values of styrene in
the chromatogram with styrene addition and in the chromatogram of the sample. You
can find this analysis procedure in literature under the designation elevation method.

Protocol:
The protocol contains
- Brief description and theory of the used method
- All weights and documentation of the preparation
- Graph showing the calibration with standard addition
- Determination of residual styrene in polystyrene sample
- Discussion and evaluation of the result as well as error discussion

E3: Identification of polymers with simple means

and with IR spectroscopy (ATR technique)
A) Identification with simple means
1. Introduction
Due to the multitude of different polymer materials in a wide variety of applications it i
soften required to identify the class of chemical compound of a polymer with simple
means.

2. Basics
Macromolecular compounds are distinguished by their chemical composition, molar mass
and molar mass distribution. For the determination of the chemical composition (similar as
for low-molecular organic compounds) there are besides some special methods the element
analysis, NMR spectroscopy, IR and UV/VIS spectroscopy, mass spectrometry as well as
pyrolysis gas chromatography.

Often it is required for the natural scientist that a fast assignment of a polymeric material
to a class of chemical compound is achieved. For this purpose there are simple means and
tests as burning properties in the flame or the thermal decomposition in a glowing test.
From burning properties, smell and the acidic or alcaline reaction of the decomposition
products conclusions can be drawn with respect to the chemical composition of polymer
materials.

The thermal load of polymeric materials leads in some cases to the opposing process of
polymerization (thermal depolymerization), most often, however, a thermal decay and a
formation of characteristic decomposition products occurs.

3. Task
a) Identify 5 different polymer samples by investigation of the burning properties and
their decomposition products.

b) Record IR spectra of these 5 polymer samples (for details see part B) and try to draw
conclusions concerning the chemical structure. Discuss and compare
1
 your findings concerning identificaton by simple means, molecular structure,
microstructure, and macroscopic properties.

4. Instructions
a) Identification of polymers with simple means:

Try to conduct suitable burning experiments with the polymer samples as burning
properties and investigation of decomposition products in order to draw conclusions for
the identification of the polymer compound class. Remember that those are technical
products, which may contain besides the polymer also inorganic filler, dye and stabilizers
maybe in high quantities. This may lead to significant deviations from the burning and
decomposition properties as reported in the literature.

As a help there are several reference polymer materials for comparison. In the appendix,
you will find some tables for the evaluation of the burning experiments. Your task will be
to compare and conclude from your observations the type of materials with help of the
presented set of information.

Some of the investigated samples are made up of rare polymer materials that might not be
decribed in the attached tables. In these cases try to collect observations and conclude as
good as possible.

Which conclusions with respect to the molecular structure are possible? How does the
molecular structure influence material properties as stiffness, ductility, crack propagation
and optical transparency?

Table of properties of the flame of some polymer types

Burnability Flame Smell of evolving polymer

product

not combustible - Silicones

pungent, as Poly tetrafluoro

hydrofluoric acid ethylene Poly trifluoro
- ethylene Poly imide

Not easily light, Phenols, formic Phenoplasts

combustible, sooting aldehyde
extinction outside Aminoplasts
the flame light yellow Ammonia, amines ,
green seem Formic aldehyde
Hydrochloric acid
Chloroprene rubber,
Poly vinyl chloride,
Poly vinylidene chloride

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burns in the bright, - Polycarbonate

flame, extinction sooting yellow,

slowly outside flame grey smoke
or not yellow/orange, - Silicone rubber
blue smoke Poly amide
dark yellow, Cellulose acetate
sooting
Burnt horn

Acetic acid

yellow Phenol, burnt paper Phenolic resin, layered

bright, very gritty Poly vinyl alcohol

decay

yellow/orange burnt rubber Poly chloroprene

yellow/orange, sweet, aromatic Poly ethylene terephtalate

sooting

yellow, blue pungent (isocyanate) Poly urethane

seam

yellow, blue Paraffine Poly ethylene,

core Poly propylene

bright, Penetrating odour Poly ester resin

sooting

1
 Highly inflammable, bright, Sweet (styrene) Poly styrene

burns outside sooting

the flame dark yelow, Acetic acid Poly vinyl acetate

slightly sooting

dark yellow, Burnt rubber rubber

sooting

bright, Sweet, fruity Poly methyl methacrylate

blue core,

crackling

blueish Formic aldehyde Poly oxymethylene

dark yellow, Acetic acid, Cellulose acetobutyrate

slightly sooting Butyric acid

light green, sparks Essigsäure Celluloseacetat

yelow/orange Burnt paper Cellulose

light, intensive Nitrous oxide Cellulose nitrate

Table of pH value ranges of the combustion products of some polymer types

pH value ranges 0.5 - 4.0 5.0 – 6.5 8.0 – 9.5

Polymer Polyester resin PUR Silicone PA

elastomeres PP PAN

Cellulose acetate PE Amino resin

Cellulose nitrate PET PS Phenol resin

PVC Epoxy resing ABS

PTFE PVAc

PVAl

PMMA

PC

Cross- linked PUR

2
b) Identification with FTIR spectroscopy

The IR spectroscopy is used especially in the qualitative analysis and for structure
determination. In the routine analysis the tests of identity and purity have priority
e.g. in the pharmacy. Furthermore this method is used for the identification of unknown
compounds and in the structural analytics for elucidation the ratio of symmetry and
bonding in a molecule.
Generally you can formulate the following three tasks:

- Check if two substances are identical

- Monitoring of chemical reaction (change of functional groups during the
reaction)
- Identification of functional groups (structure determination)

A spectrum of a sample and a reference substance will be recorded under the same
conditions to compare the identity of two substances. When both spectra are similar, you
can assume that both substances are identical. Because in an IR spectrum you can find
most of the bands in the area from 1500 cm-1 to 600 cm-1, exactly this area is interesting
for a comparison of the spectra. Therefore this area is called fingerprint region (Figure 1).
There are also commercial catalogues and spectra collections of different companies
available, which you can use for comparison.

The question, if a chemical reaction took place, is a special type of substance

identification by comparison the spectra. For it the IR spectra of product and reactant are
used (recorded under the same conditions).

A structure determination with the help of IR spectroscopy is complicated and includes

the search of the functional groups and the structure. Often other methods (NMR
spectroscopy, mass spectroscopy) except the IR spectroscopy have to be used.
The basis for the interpretation of IR spectra is the empirical finding, that functional
groups can be assigned so called group frequencies. Also each molecule has a for its
skeletal structure typical skeleton oscillation pattern.

The attribution of a band in an IR spectrum takes place via the location of the bands,
which were ascertained empirically and are compiled in a so called correlation table. At
the assignment you have to regard recording, sample preparation, states of matter,
possible interactions and temperature, because they can cause to deviations. In addition to
the location of the bands also the band intensity and the band with are interesting.

When an IR spectrum exists, you try at first to identify the setup of the molecular structure
(chains, cycles, aromatics, ..) and the carbon bonding (single bond,

2
multiple bond). The typical bands of the spectrum will be compared with the data in the
correlation tables. Helpful are also block tables in which the group frequencies of
functional groups are compiled.

Afterwards the functional groups and structures will be closer identified. Thereto detailed
correlation tables are necessary. The examining band, which should be typical for a
functional group, will be compared with the data in these tables. For comparison the band
location, the band intensity and the band shape are used. You have to distinguish key
bands from control bands. The typical key band has to exist for the corresponding
structure. The control bands are necessary for the backup of the result. Even when
supposed bands are not available it is possible to draw conclusions. The structure of the
compound will be designed under consideration of all found structural features. Finally a
comparison with a reference spectrum (library of spectra, spectrum reference substance)
has to be taken. The group frequencies and the fingerprint pattern will be adduced.

Figure 1: schematic view of an IR spectrum

The steps for the interpretation of spectra can be summarized as follows:

- setup of the molecular structure

- search for functional groups
- check of the key bands and control bands
- draft of a structure
- comparison with reference spectra

2
A possibility for determination offers the FTIR especially with the “comfortable” technique of
ATR (see below).

-Which advantages and disadvantages does the ATR technique have?

Method

Use the delivered software from the company Nicolet to inform yourself.

- Open the programme [OMNIC 7.0].

- Click in the menu bar ´Help`, ´First steps`, ´Handbook for FTIR`

Familiarise yourself with the basics of FTIR spectroscopy and the

fundamental construction of your measuring system in the “Beginner
´s Guide to FT-IR”.

- Close the “Beginner´s Guide to FT-IR” with [EXIT].

The corresponding lecture will inform you about the specialities of the ATR technique
(attenuated total reflection).

Equipment and chemicals

FTIR spectrometer: iS20 from the company Nicolet with ATR additional
unit ´Golden Gate` (Golden Gate is a single bounce diamond
ATR accessory)

Software: OMNIC

Polymer samples

Test execution

Preparation of the measuring system

- The spectrometer is on and the measuring software OMNIC is already

started
(see above).
- Open in the menu bar the point ´measurement` and then the subitem
´experimental parameter`.
- Check if the measurement settings in the menu are correct:
- Number of scans: 32
- Resolution: 8 cm-1
- Format is in % reflection
- Confirm with <OK>.

2
Spectra recording

Measuring the underground

Loosen the cover from the window of the Golden Gate and start via ´Menu bar “Measurement”
Recording the Background` or via the symbol ´Recording the Background` on the left side the
measurement of the underground with <OK>.
Add
the underground spectrum to Window1 after the finished measurement.

Measuring the samples

- Place the polymer sample with the help of tweezers on the window.
Attention! Don´t touch the crystal with the tweezers!

- Close the Golden Gate and pressure the sample with a dynamometric key.
- 40.0 cNm should be adjusted at the dynamometric key.
- Confirm the measurement via ´Menu bar “Measuring” “Recording Sample”
or via the symbol ´Recording Sample` on the left side. Fill in a spectra title and
start the measurement with <OK>; <OK>.
- Add the spectrum to the window after the measurement ended.
Hint: To remove the spectra (underground, other substances) from the spectra
window you have to click on the Pull-down-Symbol at the
window below the action bar; you have to choose the underground
spectrum (red colour) and you have to choose from the menu bar the
point “Action” “Deactivate Spectra”.

Interpret the recorded spectrum.

Which polymer could it be?

Where in the spectrum can you recognise characteristically bands?
Can you assign the bands (peaks) specific functional groups? For the
interpretation of the bands location you can use:
- assignment table for polymers (on your workstation)
- “OMNIC IR Interpretation Guide” which you find at
´Programs`”Thermo Nicolet” ´OMNIC IR Interpretation Guide`
- Close the window [peak search]
Hint: Don´t replace the original spectrum!

- Unscrew the middle screw of the Golden Gate and remove the sample.

- Record under the same conditions and as described above the spectra of the
other unknown polymer samples and identify the samples.
- Use for each new sample a new window. Sample number and window
number

2
 should be the same.
Menu bar “Window” ´New window` <OK>

Save the spectra

Save the original spectra as a group after finishing the recording of all spectra.
Thereto all spectra have to be inserted in a new window:

- Menu bar “Window” “New window” <OK> Via menu bar ´Window`
´#Window#` open the corresponding window from where
the spectrum should be copied
- Menu bar ´Editing` ´Copy`
- Via menu bar ´Window` “#Window#” open the corresponding window in
which the spectrum should be copied
- Menu bar ´Editing` ´Insert`
- After all spectra are copied in one window, mark all spectra via menu bar
´Editing` “Choose all`
- Save the spectra:
Menu bar ´File` Save group` in “Praktikum/PMS/Gr##”
- Close the OMNIC software.

2
Protocol:
The protocol contains
- Brief description and theory of the used method
- All observations of testing with simple means and conclusions from it
- Interpretation of the obtained IR spectra
- Discussion and evaluation of the results from both parts as well as error discussion
- the answers of the questions in this manual

2
 E4 Thermogravimetry

E4: Thermogravimetry
1. Introduction

To understand the interrelationships between synthesis and structure or structure and

properties is the aim of the characterization of polymers. The theoretical fundamentals forming
principles of low molecular chemistry. These are expanded by the specific features that arise
by the number and type of the monomeric linkages. Polymers can be characterised by several
parameters, which are due to their high molecular weight. These include a high viscosity of
melts and solutions, rubber elasticity, film formation and swelling. Properties of copolymers
are also influenced by their composition.

Thermo gravimetric analysis or thermal gravimetric analysis (TGA) is a method of thermal

analysis in which changes in physical and chemical properties of materials are measured as a
function of increasing temperature (with constant heating rate), or as a function of time (with
constant temperature and/or constant mass loss). TGA can provide information about physical
phenomena, such as second-order phase transitions, including vaporization, sublimation,
absorption, adsorption, and desorption. Likewise, TGA can provide information about
chemical phenomena including chemi- sorption, desolation (especially dehydration),
decomposition, and solid-gas reactions (e.g., oxidation or reduction). Today the thermo
gravimetric analyses will be realised at thermo balances, which allow the simultaneous
acquisition of TG, DTG (differential thermogravimetry) and DTA (differential thermal
analysis). The experiment can be done in different atmospheres at normal pressure or in a
vacuum.

2. The Basics

With the help of thermogravimetry the mass respectively the mass changes of a sample will be
recorded as a function of temperature and/or time (figure 1). The sample will be filled in a
fireclay crucible of inert material e.g. platinum or aluminium oxide and will be heated (heating
rates up to 100°C/min) in an oven after a defined temperature program and selected
atmosphere (up to temperatures of 1100°C; max. 1600°C). The sample holder is linked to a
microbalance, which registers the mass changes during the heating-up process. A thermal
element near the crucible measures the temperature. In general the sample will be decomposed
during the measurement.

Figure 1: Structure of a thermogravimetric balance

1
 Thermogravimetry

The thermal balances can be burdened with maximal 1 g and they have a resolution of 1 µg. It
is possible to follow all processes with a change in mass (e.g. loss of moisture, decomposition
of the polymer, oxidation of carbon).
A thermo balance can be used for quantification of material compositions (e.g. amount of
plasticiser, filler content, soot content) and for determining of decomposition kinetics
(decomposition speed, activation energy) of e.g. plastics. Furthermore the vaporisation of
moisture or solvents can be determined, which can be relevant for the assembly time detection
of colours, varnishes and adhesives.
TGA measurements will be realised under a defined gas atmosphere. It can be an inert gas
(e.g. nitrogen) or a reactive gas (e.g. air or oxygen), which flows around the heated sample.
A change of the purge gas from nitrogen to oxygen at a temperature of 600°C will be in
progress for e.g. a soot content measurement. Below 600°C the polymer will be decomposed
inert (pyrolysis) but the soot (carbon) will yet not be dismantled. This will be oxidised by the
oxygen contained in the air, inert residues are left. At temperatures above 600°C further
reactions e.g. decomposition of carbonates can take place also under inert gas.
To determine the highest loss of mass the mass [%], the derivation of the mass [%] with
respect to time (DTA) and the degradation rate [mg/min] will be pictured. The DTA curve
enables a better separation of single steps of complex reactions. Small or bad recognisable
increments in the TG curve will be illustrated in the DTA curve as peaks of which the initial
and the end temperature of a step can be determined. The temperature of the DTA peak
maximum is equivalent to the temperature of the maximal reaction conversion.
The evaluation of a typical TGA diagram with several mass conversions shows figure 2:

Figure 2: TGA diagram with several mass conversions

2
 Thermogravimetry

You can win information about the following processes:

L Decomposition
L Desorption
L Adsorption
L Vaporisation
L Sublimation
L Oxidation
L Reduction

The TGA has practical meaning at following applications:

L Determination of the concentration of water, plasticisers, volatile components

L Determination of the concentration of fillers and reinforcements
L Determination and process of the decomposition behaviour
L Determination of the thermal stability and oxidation resistance
L Determination of the drying times respectively temperatures

An accurate determination of the temperature during the TG measurement is difficult because

the thermal element mostly isn´t in a direct thermal contact with the sample. For the
temperature calibration of a thermal balance the temperatures of chemical reactions are not
suitable because they depend on the same parameters (type of gas, pressure of gas, heating
rate) like the deviations of the temperature sensor. Instead ferromagnetic alloys are used that
change their magnetic properties reversible and reproducible at the Curie point and whose
transformation temperature isn´t affected by pressure and the gaseous atmosphere. At
simultaneous DTA/TG equipment the problem of temperature calibration is disarmed because
than substances can be used which don´t provide a change in weight but a change in enthalpy.
The calibration is valid for the DTA and the TG gradients.
Changing the buoyancy force during the heating and cooling causes to low mass changes
in the TG curve that can be registered in a blind trial with the reference sample. A solid sample
with the volume V experiences in a gas of the density ρ the buoyancy force
FA = V∙ρ∙g (1)

It is for the isobar temperature dependency of the density of an ideal gas

ρ (T0) ∙ T0 = ρ (T) ∙ T (2)

From (1) and (2) follows for the mass change Δm at a change in temperature from T0 to T

Δm = m(T0) – m(T) = [FA(T0) –FA(T)] ∙ (1/g) = V ∙ [ρ(T0) –(T)]

Δm = Vρ(T0) ∙ [1 – (T0/T)] (3)

3
 Thermogravimetry

The thermal gravimetry is often executed as an essential preliminary test for DSC to ensure that
the sample will be heat-resisting in the desired measuring zone because degradation processes
or vaporisation of residual solvents can not only adulterate the measurement but also damage
the sensitive measuring head. A rule is, that it is only allowed to measure till the temperature of
the 5% decomposition in the DSC. Measuring instruments for the TGA can be linked with
other analysis instruments e.g. for product gas analysis (FTIR spectrometer, mass
spectrometer).
3. Task

Recording and interpretation of a TG measuring curve of an elastomer at EPDM basis with

different fillers (soot and chalk). Determination of the soot percentage and the chalk
percentage. Describe the watched effects in the measuring curve with appropriate reaction
equations.

4. Experimental procedure

For the thermogravimetric analysis the sample will be weighted in an Al2O3 crucible and
afterwards heated up in a nitrogen flow (20 ml/min) from 30°C to 900°C with 10 K/min. At
800°C there will be a change from nitrogen to synthetic air. The weight reduction of the
sample will be detected internal with a balance and will be recorded with suitable software on
the PC.
Execution of the TG measurements with the following measuring parameters:
L Sample mass (initial weight): approx. 25 mg
L Crucible material: Al2O3 (corundum)
L Maximal temperature: 800°C
L Heating rate: 10 K/min
L Gas atmosphere: nitrogen; at 800°C switch to synthetic air

The resultant TG curves will be corrected with a on a reference sample (empty Al 2O3 crucible)
conducted flotation measurement. The characteristically temperatures will be determined with
the help of the evaluation programme.

4.1 Sample preparation

In general sample quantities in the dimension of a few mg are enough for combined DTA/TG
measurements. At this low sample quantity it is always necessary to question if the amount
represents the entirety of the sample. The rubber sample (slice Ø 4 mm) will be taken from a
EPDM foil (d 1,5 mm) by a drill for stopples.

Open sample container of aluminium oxide will be used for the measurements. The sample
will be weighed in (25-30 mg). The better the contact between the sample and the crucible is
the less the result will be impaired by heat leaks. The correcting measurement will be realised
with an empty Al2O3 crucible under identical measurement conditions (temperature
programme, gas flows). Nitrogen and synthetic air are available as gases.

4
 Thermogravimetry

4.2 Operation of the TG device

As the measuring device a TG 209 F1 “Iris” from the NETZSCH Gerätebau GmbH is
available. The belonging thermostat has to start running at least 60 minutes before the
beginning of a measurement (normal in continuous running duty).

4.2.2 Handling of the software / enter the experiment

- Switch on the computer/ Change to Netzsch Proteus 6/ start TG_209F1_Iris on USBc 1/

open file “Korrektur_140209”
- First folder:
o Messmodus: Probe+Korrektur
o Proben-ID: Praktikum xy
o Probenname: EPDM
o Probenmasse: x,x mg
o Tiegelmasse: 162,34 mg

o Dateiname: E:/Praktikum/EPDM_Gruppe_dat
- Second, third Folder: no Change
- Fourth Folder:
o Temperature program 30800°C N2; 800-900°C N2+O2
o 10 K/min
- Last folder : control „Dateiname”
- Press the button “weiter ” (down right hand side)
- A small window opens first you have to press “tara”, then “START”
- Data acquisition starts and show you the residual time
5. Analysis

5.1 Start evaluation

o Start the program “Proteus Analysis”

o Open data file (choose before “TG 209 F1 Iris Messungen”)
o Change to temperature depend data; chose  on the y-axis the change in mass will be
indicated in %
5.2 Determine the amount of pyrolysis

For the given sample there are no mass losses via drying effects to regard. Therefore the mass
loss under inert gas to 550°C (1. step) traces back to the pyrolysis of organic material parts
(polymer, flexibiliser, lubricant etc.). The measuring curve with the step in the curve
progression will be activated via clicking (change of colour to white).

Button “Masseänderung” ö “Anwenden” 

Two boundary marks appear and they will be placed with the help of the cursor on the left and
right side of the step.
Button “Anwenden”  change of mass will be displayed in % “Ok” 

5
 Thermogravimetry

Via “1.Ableitung” you receive the first derivative of the measuring curve. The peak of this
curve is equivalent to the decomposition temperature of the polymer component. To determine
this you have to activate the temperature curve (see above), you have to position the mark on
the peak and you have to read the temperature from the cursor coordinates.
5.3 Determine the amount of chalk

The amount of chalk is equivalent to the mass loss under inert gas to 800°C (2. step). The
decomposition of chalk takes place in general between 650 and 800°C as an endothermic
process (ΔRH = 178kJ/mol). The determination is analogues to the amount of pyrolysis, only
that for this the belonging step of the change in mass will be evaluated. The measuring curve
will be activated again via clicking (change of colour to white).
Button “Masseänderung” ö “Anwenden” ”ok”
Two boundary marks appear on the left and on the right side of the activated peak. With the
help of the cursor the boundaries will be placed (gas changeover).
Please consider the chemical reaction!
5.4 Determine the amount of soot

The amount of soot is equivalent to the mass loss, which will be measured after switching on
synthetic air. So soot combustion will be enabled. The determination is analogues to the
amount of pyrolysis, only that for this the belonging step of the change in mass will be
evaluated. The measuring curve will be activated again via clicking (change of colour to
white).
Button “Masseänderung” ö “Anwenden”  ok.
Two boundary marks appear on the left and on the right side of the activated peak. With the
help of the cursor the boundaries will be placed (gas changeover).
5.5 Determine the amount of ash

The ash is a result of the inorganic material parts (e.g. silicates, chalk, zinc oxide). The
determination is analogues to the points 5.2 to 5.4 or via the button “Restmasse”.

5.6 Data storage and printing the results

Button “File” ö “Save analysis state as ...” 

Window to save the file will be opened Save
as: D:\Praktikum\name measurement
To print the analysis results the analysis file will be saved as a *.pdf file and will be processed
at an external printer.

5.7 End of the experiment

Computer: close the programs and turn off

Remove and dispose of TG sample; close the measuring cell Close
nitrogen feed and clean workstation

6
 Thermogravimetry

Don´t turn off the measuring device!

6. Control questions

1. What are the three most important methods for thermal analysis?

2. What are the differences between the DSC and the TGA method?

3. Which method is suitable for the determination of the filler content?

4. What does exothermic respectively endothermic mean?

5. Why the purging gas at the TGA will be changed at 600 °C?

6. Can you determine the crystalline amount of polymers with TGA?

7. Explain the formation of the buoyancy effect in the TG curve when heating a sample.

8. Which sample and gadget caused parameters affect the measured signals at thermal
analysis?

7
 Thermogravimetry

7. Literature

L Domininghaus, H.: Die Kunststoffe und ihre Eigenschaften

Springer Verlag, Berlin, 1997
L Michaeli, W.: Einführung in die Kunststoffverarbeitung
Carl Hanser Verlag, München, 1999
L Ehrenstein, G.W.: Polymerwerkstoffe.
Carl Hanser Verlag, München, 1978
L Ehrenstein, G.W.: Praxis der thermischen Analyse von Kunststoffen;
Carl Hanser Verlag, München, 2003
L Widmann, G.; Riesen, R.: Thermoanalyse. Dr.
Alfred Hüthig Verlag, Heidelberg, 1984
L Hoffman, M.; Krämer, H.: Kuhn, R.: Polymeranalytik II.
Georg Thieme Verlag, Stuttgart, 1977
L W.F. Hemminger & H.K. Cammenga: „Methoden der Thermischen Analyse“,
Springer Verlag, Berlin / Heidelberg, 1989.
L DIN-Normen:
L DIN 51005: Thermische Analyse (TA), Begriffe
L DIN 51006: Thermische Analyse (TA), Thermogravimetrie

8
 Thermogravimetry
E5: Characterisation of polymers with DSC

1. Introduction

The DSC (Differential Scanning Calorimetry) is one of the most significant methods in the
thermal analysis (thermoanalysis). The term thermal analysis describes in general methods
with which the physical and chemical properties of a substance or a composite can be
illustrated dependent on temperature at defined heating rate (dynamic measurement) or
dependent on time at constant temperature (static measurement). The chief subject of DSC is
the acquisition of physical and/or chemical properties via physical changes which are caused
by enthalpical effects (exothermic, endothermic). In the DSC the heat flow to a sample is
measured as a function of temperature while the temperature of the sample is changed in a
defined way.
The term of Differential Scanning Calorimetry (DSC) is so established that it will be difficult
for the synonymous DIN term “dynamic differential calorimetry” to become prevalent. But
you should be aware that the correct term according to DIN 53 765 dynamic differential
calorimetry (DKK) is.

2. Basics

Low molecular substances change with increasing temperature their state of substance and
pass at the melting temperature visible from crystal into a liquid and at the boiling
temperature from the liquid into a gas.
The melting behaviour of polymers is different from the behaviour of low molecular
compounds. Often you can find wide melting ranges instead of clear melting points. These
besides depend deeply on the previous history of the polymer and partly only a gradually
softening instead of a melting will be observed. Also the heat of fusion fluctuates according
to sample and previous history. The reasons for all these effects are found in the size of the
macro molecules which deeply obstruct an entirely regular classification in a crystal because
of kinetic reasons and partly even entirely prevent. In this case instead of a melting
temperature a softening point (respectively instead of a freezing point a solidification point) is
observed, the so called deformation point. Below this deformation point the polymer exists as
an amorphous solid. Naturally the glass transition temperature Tg is always lower than the
melting temperature Tm. Theoretical considerations forecast a ratio of T g ~ 2/3 Tm (in K) but
the experimental data of Tg are appreciable closer at Tm.
Besides melting temperatures and glass transition temperatures yet more transition
temperatures and relaxation temperatures exist. Because these cannot be always interpreted
immediately molecular, often the at the highest temperature happening crossover is referred
to as α transition, the next lower one as β transition and so forth.

With the help of DSC it is possible to get statements about the melting and crystallisation
behaviour and the associated enthalpies, the glass transition temperature, the degree of
crystallinity or the specific heat of polymers. From the DSC measurements you get also
information about the miscibility of polymers and the

9
 Thermogravimetry
reversible and irreversible parts of phase transformation processes. Each of these crossovers
is thermodynamically given through a change of enthalpy or volume.

Thermodynamic states are described by the Gibbs energy respectively their first derivatives
after temperature or pressure e.g. through the enthalpy H, the entropy S and the volume V:

H = G - T(∂G/ ∂T)p (1)

S = -(∂G/ ∂T)p (2)

V = (∂G/ ∂p)T (3)

The second derivatives of the Gibbs energy lead to heat capacity Cp, cubic expansion
coefficient α and isothermal compressibility κ:

Cp = (∂H/ ∂T)p = T(∂S/ ∂T)p = -T(∂2G/ ∂T2)p (4)

α = V-1(∂V/ ∂T)p (5)

κ = -V-1(∂V/ ∂p)T (6)

Figure 1: Schematic representation of different thermal transformations: melting

process as a thermodynamic transformation first-order, rotation transformation as a
thermodynamic transformation second-order; l= liquid, cr= crystal, am= amorphous
state [G. Rehage and W. Borchard]

1
 Thermogravimetry

Figure 2: DSC diagram of deterred polyamide; Tg= glass temperature, Tc=

recrystallisation, Tm= melting temperature

Thermodynamic transformations can be characterised by the corresponding changes of these

state variables. You have to distinguish between thermodynamic transformation first-order
and second-order. Both types of thermodynamic transformations are characterised by
thermodynamic states of equilibrium to both sites of physical transformation temperatures.
Figure 2 shows a DSC diagram with the three at polymers observed characteristically
temperatures Tg, Tc and Tm. While Tg and Tm are gained from the heating-up curve, Tc is
determined from the cooling curve. Not all three temperatures are measurable at all polymers.
The signal intensity for T g and Tc depends on the respective crystallisation tendency. So at
highly crystalline polymers Tg is only difficult to non-determinable, while at mainly
amorphous polymers the same applies to T c. Further the effect of different glass temperatures
can emerge at semi-crystalline polymers: big amorphous areas have a lower Tg than small
between crystalline regions trapped areas. These different glass transition temperatures cause
in the experiment a smearing of the glass transition step so that this is only badly discernible
and goes down in a slight buckling of the baseline in the extreme case.
The melting temperature of polymers T m is often near respectively above the temperature at
which the thermic decomposition starts and is for this reason not measurable.

2.1 Glass transition temperature

1
 Thermogravimetry
The glass transition temperature Tg is the temperature at which amorphous or semi-
crystalline polymers pass from the liquid or rubbery-elastic state into the hard-elastic or
glassy state or conversely. Cause for this phenomenon is the freezing respectively thawing of
fractional Brownian motion of longer chain segments of the polymer (rotations, translations).
When reaching the glass transition temperature a drastically change of viscosity as well as
other physical properties including also the enthalpy and entropy of the polymer occurs. In
the case of a semi-crystalline polymer then only the amorphous part is affected. The glassy
state emerges accordingly at not or only little crystallisable polymers. Polymers with good
crystallisation ability can be only transferred into the glassy state when they will be cooled
down quickly i.e. when they will be chilled.

The glass transition has many features of a thermodynamic transformation second derivative.
However it is a kinetic controlled and not a thermodynamic transition because there exists no
equilibrium to both sites of the transformation temperature. Factors that affect the glass
transition temperature:

 The heating respectively cooling rate of the sample: The smaller the cooling rate
the lower is the glass temperature.
 The mobility of the polymer chain: Voluminous substituents interfere the bond
rotation of the main chain respectively the more the rotation of the main chain is
restricted the higher is Tg. The rotation of the main chain is favoured when the energy
differences between gauche and trans conformation is only small.
 The length of the side chains: The longer the side chain the lower is the glass
temperature because only the first link of the side chain interferes the rotation around
the main chain. Long side chains act like added plasticisers.
 Intermolecular forces: Intermolecular forces can increase the glass temperature. You
can observe especially strong effects at polymers that contain polar groups.
 Flexible substituents: favour the bond rotation and lower Tg
 Cross linkings: interfere the bond rotation; Tg increases
 Arborisations: decline the packing density and favour the bond rotation; Tg
drops
 Plasticisers: Plasticisers (e.g. residual monomers, solvents, etc) usually lead to a
lowering of the glass temperature.
 Pressure: With increasing pressure also the glass temperature (approximately
20 K per 1000 bar) increases.
 Molar masses: The glass temperature is inversely proportional to molar mass.

2.2 Melting and crystallisation behaviour of polymers

A typical thermodynamic transformation first derivative is e.g. the melting. Polymers with
their characteristically molecular mass distribution and irregular crystallite

1
 Thermogravimetry
formation have a wide temperature range for melting respectively crystallisation. Semi-
crystalline polymers remain solid when heated until the melting of their crystalline areas. The
melting process manifests itself as an endothermic peak in the DSC curve. The temperature
when melting the last crystallites is called melting point. This is the temperature at the
maximum of the peak. The area below is equal to the enthalpy of fusion of the sample.
Between the crystallites remain amorphous areas i.e. there is no complete crystallinity. The
crystalline part in a polymer is depending on the chain length, the degree of arborisation, the
tacticity, the type of crystallisation and on the concentration of additives. The different areas
are not in a thermodynamic equilibrium rather the polymer is stabilised by kinetic inhibitions.
Hardness and stability of the polymer grow with increasing crystallinity. The crystallinity will
be determined by comparison of measured specific enthalpy of fusion and of specific
enthalpy of fusion of crystallites
i.e. of the complete crystalline polymer. Usually it is between 20 and 75%.
Only in the maximum of the melting peak you can assume that all crystalline areas are
melted.
Factors that affect the melting point:

 Steric effects by voluminous side groups: Big side groups reduce the chain agility and
increase the melting point.
 Chain stiffness: The presence of -O- and -(CO)- groups lower the melting point while
phenylene groups increase the melting point.
 Polar groups: increase the melting point by implementation of further intermolecular
interactions.
 Molecular weight: The chain ends express defects which will not be implemented in
the crystals. At a small molecular weight the number of chain ends is big and
therewith also the defect concentration is high. This lowers the degree of
crystallisation.
 Arborisations: Chain pieces with arborisations do not crystallise. A high concentration
of arborisations implicates a reduction of the degree of crystallisation and a reduction
of crystallites. The melting point decreases.

2.3 Measurement process

DSC devices basically consist of two parts - the heating block (oven) and the registration
unit. In the heating block sample and reference are placed after they were trapped in a metal
crucible (usually aluminium pan). Classic DSC devices work with the help of a twin
measuring arrangement (see figure 4 and 5). (There are also triple

1
 Thermogravimetry
arrangements.) It is distinguished between two measurement processes.

A) Heat flux differential scanning calorimetry (heat flux DSC)

At the heat flux DSC the difference in temperature ΔT and the resulting changes in heat flow
ΔQ between sample and reference during heating are measured. The advantages of this
method are the more robust design of the devices, the convenient handling and the stable
baseline of the measuring curves. According to this method the provided measuring device
works.

Figure 4: Sketch heat flux DSC measuring cell; TR= temperature of the reference, TS=
temperature of the sample, QOR= heat flow from the oven to the reference, QOS= heat flow
from the oven to the sample

B) Power compensating differential scanning calorimetry (power

compensating DSC)

At the power compensating DSC the measuring cell consists of two separated ovens. The
temperature difference between sample and reference will be reduced to zero through the
different heat outputs of the ovens. The measured heat output difference ΔP is equivalent to
the change of heat flow ΔQ between sample and reference.
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Figure 5: Sketch power compensating DSC measuring cell; TR= temperature of the
reference, TS= temperature of the sample, PR= heat output of the reference oven, PS= heat
output of the sample oven

The measuring principle is that both the to be measured sample and also a reference (mostly a
with air filled pannikin) will be heated up or cooled down together in the oven with the help
of a temperature programme where both have steadily the same temperature. Thermocouples
make sure at each time of measurement that there is no temperature difference between both
cells. This method is particularly adapted for very fast reactions because the small ovens don
´t react so sluggish.
You get almost the same information from both methods and therefore they are summarised
as DSC in common parlance.
When knowing the heat content of the reference you can calculate from the change of heat
flow ΔQ also the heat content, the enthalpy and the heat capacity of the sample. As mentioned
above the heat flow to the sample Q Ṗ is proportional to the temperature difference ΔT. The
constant of proportionality has to be determined by a calibration. For this the consideration of
thermodynamic transformations with known enthalpies is suited. Normally you are measuring
the heating sale when melting high purity metal samples for example of indium, lead, tin or
zinc of which the specific melting enthalpies are known.

2.4 Physical – chemical reasons for DSC peaks

With DSC measured effects can have the following reasons which are summarised in a table.

2.4.1 Physical reasons

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Reason Effect

endothermic exothermic

Melting +

Crystallisation +

Evaporation +

Sublimation +

Adsorption +

Absorption +

Desorption +

Curie point transitions +

Liquid crystal transitions +

Tg No peaks, only offset of the heat

flow curve
cp

2.4.2 Chemical reasons

Reason Effect

endothermic exothermic

Chemisorption +

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Desolvation +

Dehydration +

Decomposition +

Oxidative degradation +

Redox reactions + +

Solid-phase reactions + +

Combustion +

Polymerisation +

Hardening, cross-linkage +

Catalytic reactions +

3. Task

Become acquainted with the measuring device, its periphery and the basics in the usage of
modern evaluation software.
You have to determine the glass transition temperature, the melting behaviour and the
crystallisation behaviour of polyethylene terephthalate by use of DSC in the temperature
range from 25°C to 280°C after a given temperature programme. The received heating curves
and cooling curves have to be evaluated and the results have to be discussed. Two heating
curves of the sample have to be measured.

4. Test execution

4.1 Sample preparation

In general sample quantities in the dimension of a few mg are enough for DSC
measurements. At this low sample quantity it is always necessary to question if the amount
represents the entirety of the sample. The polyethylene terephthalate sample (slice Ø 4 mm)
will be taken from a beverage bottle by a drill for stopples.
Sample containers of aluminium will be used for the measurements, which are produced as
disposable crucibles. The sample will be weighed in (approx. 4 mg). The better the contact
between the sample and the crucible is the less the result will be impaired by heat leaks. As a
reference an empty crucible is used. Before closing with a crucible press the crucible lid will

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be pierced by a needle to enable an interchange

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of gases with the atmosphere of the measuring cell. On the one hand vapours which the
samples produce at higher temperature (moisture, solvent residues, plasticiser, monomers)
can escape and on the other hand the trapped air can be replaced by the purge gas nitrogen.
Using nitrogen as purge gas is recommended under the aspect that the samples should be
measured several times. The differences between the first, the second and the third temper
cycle indicate the thermal background (inventory effects, tensions, vaporisation of volatile
components) and show the influence of different temper speed. Furthermore the sample has a
better thermal contact to the crucible after the first heating-up. This is the reason why in
general the first heating cycle will be considered separately in the evaluation.
Attention! For an optimal thermal contact with the sensor plate you have to pay attention
that the crucible bottom is free of scratches after the grouting.

4.2 Operation of the DSC

device Safety instructions:

 Control the tubes that they are assured with hose clamps.
 Never switch off the device at high temperatures because the environment of the
measuring cell can be heated up uncontrolled due to the absence of ventilation.
 Never touch the oven, the oven lid or a just removed sample! The oven can reach a
temperature of 700°C. Use tweezers to insert or remove lid or sample.
 If the evaluating substances build toxic gases than the device should be used under the
fume cupboard.
 Inform your supervisor when there are upcoming problems.

4.2.1 Preparation

A DSC 200 of the NETZSCH Gerätebau GmbH is available as the measuring device.

 Control that the measuring device is on – LED “on line” shines green
 The measuring cell has 3 lids (device lid + 2 sample room lids) which will be
removed with tweezers.
 The closed sample crucible will be inserted. At the sensor plate are two heat flow
sensors visible. The sample crucible has to be inserted on the mid left (see marks on
the device) and the reference crucible (empty closed crucible) on the mid right.

Attention! Don´t scratch the sensor plate with the tweezers!

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 After insert the crucibles the measuring cell will be closed again with the three lids.
 Open the nitrogen supply. Activate the gas supplies “protective” and “purge 1” (LED
´s green). (Flow rate protective - 50 ml/min and purge 1 - 20 ml/min)

4.2.2 Software operation/Enter the experiment

 Switch on the computer

 Open DSC 200
 Open file DSC 200 Messungen/Praktikum/PET
 Window 1 – “DSC 200 Assistant”
Measuring mode: sample attempt ID: fill in sample mass: xx.x mg
“Next” 
 Window 2 – “Head of the measurement”
Operator: Max Mustermann “Next”

 Window 3 – “Definition of the DSC 200 temperature programme”
Temperature programme will be adopted unchanged
A heating-up rate of 10 K/min at the analysis has proved. For cooling down
three different speeds were chosen.
“Next” 
 Window 4 – “Define the file name for the measurement”
File name: Max Mustermann
“Save” 
 “Insert sample now” (is already done see above)
“Ok” 
 “DSC 200 comparison ...”
“START” 
 Window 5 – “DSC 200 ... Measurement”
Record of the measuring signal and the temperature against the time until the display
“end of measurement (normal)”
“Ok” 

5. Evaluation

5.1 Start evaluation

Button “tools” 🠂 “start evaluation programme”

 Proteus software (NETZSCH Thermische Analyse) for evaluation will be started and the
measuring curve will be adopted

Button “settings” 🠂 “segments”  window segments opens

With the exception of the three dynamic heating-ups (red arrow) deactivate all other segments
( click🠂) 🠂 “ok” 

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Only the heating-ups of the DSC peaks respectively DSC steps are displayed.

Button “settings” 🠂 click on “x-temperature” 🠂  appears in front of this display 🠂 “ok”

 on the x-axis the temperature is stated. The three DSC peaks lie on top of each other and
at least one heating-up curve shows a step in the DSC signal.

5.2 Determine the glass transition temperature Tg

A measuring curve with the step in the course of the curve will be activated by clicking
(colour change to white). The onset temperature or the temperature at the turning point can be
used for the indication of the glass transition temperature whereby the respective choice has
to be noted at the temperature indication.
Button “evaluation” 🠂 “onset” 
Two boundary marks appear and they will be placed with the help of the cursor on the left
and right side of the step.
Button “appliance”  onset temperature = glass transition temperature TgOnset is displayed
“ok” 
Button “evaluation” 🠂 “turning point” 
Go on as before.
As mentioned above the Tg is dependent on the heating rate! The used heating rate has to be
declared. For the determination of the glass transition temperature a heating rate of 10 K/min
is suggested whereby the start temperature should be at least 30 K below the expected Tg.

5.3 Determine the melting temperature Tm

The determination of the melting temperature is similar to the glass transition temperature
only that for this the corresponding DSC peak is evaluated. A measuring curve is activated by
clicking (colour change to white).
Button “evaluation” 🠒 “peak” 🢧
Two boundary marks appear on the left and on the right side of the activated peak. With the
help of the cursor the boundaries are placed.
Button “appliance” 🢧 peak temperature = melting temperature is displayed “ok” 🢧
Repeat the evaluation with the second and the third measuring curve.
A heating rate of 10 K/min is also suggested for the analysis of melting processes. The choice
of the start temperature depends on the melting area respectively the temperature location of
other to be measured effects. Because of the wide melting areas the start temperature should
be at least 100 K below the peak apex temperature.

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5.4 Determine the crystallisation temperature Tc

The determination of the crystallisation temperature happens similar to the melting

temperature via the corresponding DSC peak which is primary visible in the cooling curves.
Therefore the corresponding segments of the DSC diagram have to be activated (see point
5.1).
Button “settings” 🠂 “segments”  window segments opens Activate
the three segments of the dynamical cooling (blue arrow) ( click
🠂 ) 🠂 “ok” 
In addition to the heating-up of the DSC peaks respectively steps also the cooling are displayed.
A measuring curve is activated by clicking (colour change to white). Button
“evaluation” 🠒 “peak” 🢧
Two boundary marks appear on the left and on the right side of the activated peak. With the
help of the cursor the boundaries are placed.
Button “appliance” 🢧 peak temperature = crystallisation temperature is displayed “ok”
🢧
Also Tc depends on the cooling rate which has to be stated. The influence of the different
cooling speeds on the measuring results has to be discussed.

5.5 Data storage and printing of the results

Button “file” 🠂 “save analysis state as ...” 

Window for saving the file will be opened.
Save under C:\DSC 200 Auswertung\Praktikum\Dateiname der Messung (see 4.2.2) Button
„file“ 🠂 „print graphic“  printout of the results

5.4 End of the experiment

Computer: close the programmes and turn off

Remove and dispose of the DSC sample; close the measuring cell
Close nitrogen feed and clean work station.
Don´t turn off the measuring device!

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6. Control questions

1. How is polyethylene terephthalate produced?

2. Is the melting process endothermic or exothermic?
3. Name at least two methods of the thermal analysis of polymers!
4. What is determined at the DSC?
5. Which physical and /or chemical processes can underlie the measuring effect?
6. What is the glass transition temperature and which factors have an influence on it?
7. Sketch a course of the DSC curve with the typical phase transitions for a semi-
crystalline polymer!
8. What can you measure with the DSC?
9. How does a common DSC curve look like?
10. How is the enthalpy defined?
11. What do you have to note especially at a DSC measurement?
12. Why is nitrogen used at the DSC?
13. Which polymers belong to the amorphous and which to the crystalline plastics?

7. Literature

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 G. Höhne, W. Hemminger, H.-J. Flammersheim: Differential Scanning Calorimetry,
Springer Berlin 1996, ISBN 3-540-59012-9
 Tieke: »Makromolekulare Chemie, eine Einführung «, VCH, Weinheim 1997, ISBN 3- 527-
29364-7
 M.D. Lechner, K. Gehrke, E.H. Nordmeier, »Makromolekulare Chemie, Ein Lehrbuch für
Chemiker, Physiker, Materialwissenschaftler und Verfahrenstechniker, Birkhäuser Verlag,
Berlin 1993, ISBN 3-7643—5343-0
 D. Braun, H. Cherdron, H. Ritter, »Praktikum der Makromolekularen Stoffe,
Grundlagen, Synthesen, Modifizierungen, Charakterisierungen«, Wiley-VCH,
Weinheim 1999, ISBN 3-527-29756-1
 G. Widmann, R. Riesen: Thermoanalyse : Anwendungen, Begriffe, Methoden, 3.,
durchges. Aufl. Heidelberg : Hüthig, 1990
 G. W. Ehrenstein, G. Riedel, P. Trawiel: Praxis der Thermischen Analyse von
Kunststoffen, 2. Aufl. Carl Hanser Verlag 2003
 B. Tieke: Makromolekulare Chemie, Eine Einführung; Weinheim : VCH, 1997
 J. Falbe, M. Regitz: Römpp Chemie Lexikon, 9. Auflage; Stuttgart : Thieme 1995
 H. G. Elias: Makromoleküle Band I und II : Hüthig 1990
 Turi, E. A.: Thermal characterization of polymeric materials, Vol. 1 und 2, San Diego, Calif.
[u.a] : Acad. Press, 1997
 Menges, G.: Werkstoffkunde Kunststoffe, München [u.a.] : Hanser, 1998