Differential Scanning Calorimetry (DSC)

Name: Edward Flood

Student number: 01092669

Lab partner: Gary Shortall

Date: 16.04.05

Abstract:
The purpose of this experiment was to use Differential Scanning Calorimetry to find numerous thermal properties of a number of polymer samples. The credibility of the machine to be used was tested using Indium metal as a reference material. Indium was used because its melting temperature is low enough to coincide with the temperature range in which most of the polymer transitions that apply to this experiment occur. Also, it has a well-defined melting point with an accepted melting temperature and enthalpy of melting of 156oC and 28.5J/g respectively. The values obtained using DSC were 156oC and 21.445J/g, which shows that the enthalpy measurement is off by approximately 25% and the temperature measurements are about right. The polymers analysed were as follows: 1. 2. 3. 4. 5. 6. 7. Polyethylene (high density) (HDPE) Poly(Vinyl Chloride) high molecular weight (high MW PVC) Poly(Vinyl Chloride) low molecular weight (low MW PVC) Poly(Acrylic Acid) (PAA) Poly(Methyl Methacrylate) (PMMA) Polystyrene Poly(Vinyl Alcohol) (PVA)

As well as melting points and enthalpies of melting, the glass transition temperatures of the above polymers were found (where applicable) and attempts were made to account for any deviations from ideality that inevitably occurred.

Introduction and theory:

Differential Scanning Calorimetry is a technique used to measure thermal properties of polymers based on the rate at which they absorb heat energy compared to a reference material. The technique takes advantage of the energy changes involved in the various phase transitions of certain polymer molecules. This allows several properties of the material to be ascertained; melting points, enthalpies of melting, crystallisation temperatures, glass transition temperatures and degradation temperatures. A heat flux differential scanning calorimeter will be used in the experiment. This is one in which a sample is heated along with a reference material with
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a known specific heat. One of the criteria of this technique is that the sample and reference material remain at the same temperature during heating. This can be achieved by Setting the machine to heat both the sample and reference material at a specific rate (In this experiment, the rate is set to 10oC per minute). This allows the heat flux or difference in energy input between the sample and reference to be measured. Maintaining a constant supply of heat to both materials would not (unless the materials have the same heat capacity at all points, which is unlikely) maintain a minimal temperature difference between them. Instead, a computer is connected to the machine, and using the software and various signals from the calorimeter, decides when to supply heat to either material. This information is then dealt with by the computer software and presents it as a graph of the energy changes versus the temperature. A standard DSC curve for a particular polymer is shown in fig. 1.

Fig 1. A standard output for a polymer from a DSC machine.

From the diagram, it can be seen that a sudden upward jump in the curve signifies an exothermic process. A sudden drop in heat flux indicates an endothermic process. It is possible to approximate the heat flow into the sample holder using the following equation:
dQ = K ( Tb T ) ..(1) dT

T is the sample temperature Tb: programmed block temperature

K: thermal conductivity of the material

Tb = T0 + qt ..(2)

T0 is the initial temperature and q is the programmed heating rate. The heat capacity is defined as the amount of heat energy required to raise the temperature of a body by 1K. For a substance with a constant heat capacity:
Q = C P ( T T0 ) ..(3)

It is possible to derive an equation from equations 2 and 3 that forms the basis for the DSC experiment. This is as follows:
T = q CP ..(4) K

T is the difference in temperature between the reference material and the sample. The heat capacity is given as
C P = mc P ..(5)

Where cp is the specific heat (Amount of heat required to raise the temperature of unit mass by 1K). The enthalpy change for a given phase transition may be found by integrating over the area in which the transition is seen to occur on the DSC plot. This change may be described by the following integral:
KT H = C P dt = q dT ..(6) Ti Ti
Tf Tf

Where the limits of integration Ti and Tf are the initial and final temperatures over which the graph is integrated. Therefore it is the area under the curve that gives information about the enthalpy changes involved in the various transitions.

Some transitions can be identified at certain temperatures, and the following paragraphs include short descriptions of these transitions, the order in which they occur, and their significance at a molecular level. Glass transition temperature, TG: This is the point at which, on heating, an amorphous polymer changes from being hard, brittle and glass like to being a soft rubber like substance. In a way, this is analogous to a percolation threshold. As the polymer is cooled, molecules have less freedom and become bonded to each other. As the percentage of bonded molecules increases, there comes a point at which long-range connectivity occurs (the percolation threshold) and the polymer reverts to a glass like phase again. This point may be identified as a dip on a graph of heat flux versus increasing temperature, this is due to the molecule having a greater degree of freedom and absorbing energy to maintain the same rate of heating as the reference. It can then be concluded that glass transition is an endothermic process. Unlike a transition from a solid to a liquid, or liquid to gas, the energy change involved in glass transition (a second order phase change) is quite small. Fully crystalline polymers have no glass transition and their structure remains intact until the melting point. The following table is a list of factors relating to polymers and their effect on the glass transition temperature: Decreasing Tg Caused by: Main chain flexibility Flexible side chains Increase in Tacticity Increased symmetry Branching Addition of plasticisers Or diluents Increasing Tg Caused by: Main chain rigidity Bulky or rigid side chains Increased cohesive energy density Increased molecular weight Increased polarity Cross linking

Temperature of crystallisation, TC: Continuing to heat a polymer past its Glass transition temperature eventually leads to another transition. Before this point in the thermal analysis, the
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molecules are arranged in a random fashion and are coiled around each other in an unfavourable manner. A transition occurs when molecules acquire enough freedom to move into a more energetically stable phase, i.e. a crystalline state. This would indicate that the phase following the glass transition is metastable and when sufficient energy is supplied, its molecules adapt a more stable (lower energy) arrangement. Because the molecules in a crystalline solid have less freedom than those in a flexible rubbery one, the transition between these two states is exothermic and may be seen as a brief upward jump in the graph. Temperature of melting, TM: This is the point at which the (now crystalline) polymer molecules have gained enough vibrational freedom to break free from the solid binding forces and form a liquid. Due to the increased freedom of these molecules, the DSC graph should take a sudden dip at this temperature to indicate the endothermic nature of the process, which is a first order transition. The melting point of any substance can be given by:
Tm = H m ..(7) S m

Hm is the melting temperature and Sm is the change of entropy involved in the melting phase (entropy of fusion). Degradation Temperature, TD: The final transition on a DSC graph is the degradation temperature, TD. At this point in the heating cycle, individual bonds between atoms start to break as the vibrations become more and more fierce until eventually, individual polymer molecules decompose into their components. Depending on the nature of the substance under investigation, this process can be either endothermic or exothermic In this experiment, the thermal properties of seven polymers will be investigated along with those of a reference material, which, in this case, will be indium metal. These are as follows: 1. Indium 2. Polyethylene (high density) (HDPE)
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3. 4. 5. 6. 7. 8.

Poly(Vinyl Chloride) high molecular weight (high MW PVC) Poly(Vinyl Chloride) low molecular weight (low MW PVC) Poly(Acrylic Acid) (PAA) Poly(Methyl Methacrylate) (PMMA) Polystyrene Poly(Vinyl Alcohol) (PVA)

The transitions listed above will, where applicable, be observed and the enthalpy changes involved in these processes will be measured by integration of areas underneath the start and endpoints of any peaks or dips on the DSC graphs. Computer software accompanying the differential scanning calorimeter will enable the enthalpy changes to be measured without the need for evaluating large numerical integrals by hand. Apparatus: Shown in fig.2 is a diagram of the workings of a differential scanning calorimeter.
Figure 2, the workings of a DSC machine:

The reference pan is to remain empty at all times. Signals from both pans provide information to the computer. This allows it to regulate the temperature and provide a constant heating rate. Not shown are the gas inlets and outlets, using these, a chemically inert gas such as Argon or nitrogen may be pumped through the machine in order to prevent the accumulation of dust. The gas also serves to remove any volatile chemicals that may be present.

Procedure: Firstly, samples were prepared for analysis. In order to avoid confusion, this was performed as the samples were required as opposed to preparing all samples at once. Extreme care was taken not to contaminate samples or sample pans with either other chemicals or matter from human skin. This meant that all equipment had to be handled with tweezers. Samples were prepared as follows: The tare weight of the sample pan and lid were obtained. Sample pans with flat undersides were selected so as to make the maximum contact possible with the bottom of the calorimeter. Following this, between 5 and 10 milligrams of polymer were placed in the sample pan and the mass of the filled sample pan and lid were found. This was the mass of polymer to be used. Again using tweezers, the sample pan and lid were moved to the crimping press whereupon crimping the lid sealed the pan. Another sample pan was weighed along with its lid. This, however, was left empty and sealed using the crimping device, forming the reference pan to be heated along with the sample. The first sample to be observed was the Indium reference material. This was placed in the left hand side of the furnace in the calorimeter while the reference pan was placed in the right hand position, where it was to remain for the duration of the experiment. Heating cycle for Indium: Nitrogen atmosphere, with a gas flow rate of 10Cm3/min, heating rate of 10oC/min from 120oC to 180oC. For the polymer samples, the heating cycle proceeded as follows: The same gas flow rate was maintained, along with the heating rate of 10oC/min. The only change was that the range of temperature was modified so that it ranged from 30oC to 250oC. Following this, the furnace was allowed cool to room temperature before the next sample could be introduced.

The resulting graphs are then analysed and information about onset, peak and endpoint temperatures and changes in enthalpy for the various processes can be obtained using the computer software. Results & analysis: Shown in table 1 are the masses of each of the polymer samples taken along with the mass of Indium. Also temperatures of glass transition, crystallisation, melting and degradation are shown along with the enthalpy changes associated with each of these.
Table 1:

Sample Name Indium Polyethylene (high density) Poly(Vinyl Chloride) High MW Poly(Vinyl Chloride) Low MW Poly(Acrylic Acid) Poly(Methyl Methacrylate) Polystyrene Poly(Vinyl Alcohol)

Mass in mg 12.7 7.1 9.2 9.5 9.7 10.3 9.9 8.1

TG (oC) n/a n/a 85.385 81.252 -103.32 -90

TM (oC) 156.9 124.92oC n/a n/a 130 -71.556 162.18

The resultant graphs are shown on the next few pages along with the enthalpy changes and temperature range of each transition. The first of these graphs is for the Indium reference material.
Graph 1:

Mass of sample: 12.7mg Enthalpy of melting: 21.4451.07J/g Onset temperature: 156.9oC Peak melting temperature: 158.41oC Polyethylene:
Graph 2:

Mass of sample: 7.1mg

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Enthalpy of melting: 118.35.92J/g Onset temperature: 124.92oC Peak melting temperature: 133.78oC Poly(Acrylic Acid):
Graph 3

Mass of polymer taken: 9.7mg Tg: Enthalpy of melting: 77.9593.9J/g Onset temperature: 130oC Peak melting temperature: 149.11oC Poly(Methylmethacryalte):
Graph 4:

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Mass of polymer taken: 10.3mg Tg: 103.32oC Enthalpy of melting:Onset temperature:Peak melting temperature:Degradation onset: 191.4oC Peak degradation temperature: 201.9oC Enthalpy: -1.4977J/g Poly(Vinyl Alcohol):
Graph 5:

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Mass of polymer taken: 8.1mg Tg: 90oC Enthalpy of melting: 43.782.2J/g Onset temperature: 162.18oC Peak melting temperature: 222.15oC Polystyrene:
Graph 6

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Mass of polymer taken: 9.9mg Tg: Enthalpy of melting: 8.26860.4J/g Onset temperature: 71.556oC Peak melting temperature: 73.84oC High MW Poly(Vinyl Chloride): Graph 7:

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Mass of polymer taken: 9.2mg Tg: 85.385oC Enthalpy of melting: Onset temperature: Peak melting temperature Low MW Poly(vinyl Chloride):
Graph 8:

Mass of polymer taken: 9.5mg Tg: 81.252oC Enthalpy of melting: Onset temperature: Peak melting temperature

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Discussion: In this section, the results will be discussed and any discrepancies between theory and experiment will be addressed: Indium: A well-defined transition is seen to occur between the temperatures of 156 and 160oC (centred on a peak of 158.41oC) with an enthalpy change for the transition of 21.4451.07J/g. The actual melting point of Indium metal is 156.0oC and its enthalpy of fusion is 28.6J/g, so it can be concluded that the transition on the graph is the melting of the sample. Polyethylene: Polyethylene is a simple straight chain polymer composed of repeating units of the ethylene molecule. Its structure is shown below:

The output graph from the DSC machine showed one distinct transition with an onset temperature of 124.92oC and a peak of 133.78oC with an associated enthalpy change of 118.315.9J/g. By comparison, the melting point of high-density polyethylene is 133.5oC. It can be seen that this is in quite close agreement with accepted theoretical values. Because Polyethylene consists mainly of saturated carbon bonds and due to the lack of anything other than weak London interactions to hold its molecules together, polyethylene has low values for both the glass transition and melting temperatures. Polyacrylic Acid: In this case, two distinct transitions may be seen. The first of these occurs at 58.82oC with a change in enthalpy of 6.94420.35J/g and it can be seen that the transition occurs over a relatively narrow range of temperature. The other transition, however, occurs over a much broader range from approximately 130oC to 200oC with a peak temperature of 149.11oC and an

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enthalpy change of 77.9593.9J/g. The structure of Poly(Acrylic Acid) is shown here:

The presence of the hydroxyl group as a substituent on the molecule should ensure that PAA has a higher melting point (due to Hydrogen bonding) than that of the more structurally simple polyethylene. This is indeed the case as the melting of this substance occurs at approximately 150oC (this is the peak value). However, the melting occurs over a large range of temperatures which could be explained in a number of ways. The most probable reason for this is that there were impurities present in the sample. Most likely a foreign object was picked up during the weighing process as the analytical balance may not have been cleaned beforehand. Also the sample may have been contaminated in the handling process, by either the tweezers or accidental contact with human skin. Another possible explanation could apply if there was a large distribution of molar masses of the polymer present in the sample. Unfortunately this cannot be verified so the blame for this must lay at human error. Also, in theory, a glass transition should occur in the region of 105oC, and in the graph, no such transition is seen, pointing further at sample contamination. Poly(Methyl Methacrylate): Two transitions are evident from the graph; firstly an onset temperature of 103.3oC leads to a peak at 112.7oC and an enthalpy change of 2.7120.14J/g. Secondly, an exothermic transition is seen to occur, beginning at 191.4oC, running through a peak of 204.9oC with a small enthalpy change of 1.49770.075J/g. The structure of Poly(methylmethacrylate) (PMMA) is shown below:

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The melting point of PMMA is taken from literature as 378K or 105oC, indicating the first transition on the graph to be a melting point. The second transition is much more interesting, however. Due to an exothermic peak at such a high temperature it may be concluded that this is the degradation temperature. Poly(Vinyl Alcohol): The most noticeable thing about the output from the sample of PVA is the apparent presence of two peaks. The first peak may be due to impurities in the material as there are no transitions in its immediate neighbourhood. The accepted melting point of this polymer is approximately 230oC (fully hydrolysed) and no other transitions are known occur in the area of 139 to 180oC. The second transition occurs from 205oC with a peak at 222.15oC and an enthalpy change of 43.7882.2J/g, meaning this is the point at which the sample melted. Also, according to references, a glass transition occurs at approximately 85oC, this can be seen as a miniscule dip in the graph at approximately 90oC. Just by looking at the structure of PVA, it becomes clear why it has such a high boiling point. The molecule itself has minimal branching and can make the most of any London interactions between molecules. These forces of interaction dont dominate, however. Hydrogen bonding is by far the dominant interaction in this particular polymer and goes some way into explaining its thermal behaviour.

Polystyrene: Polystyrene is accepted to have a glass transition at approximately 373K or 100oC. A peak is seen to occur at approximately 78oC but the nature of this transition conflicts with that of a glass transition. Because the graph is seen to dip sharply and all but rise back up to its original height, the possibility of glass transition at this point can safely be ruled out. Because Polystyrene comes in a massive variety of molar masses, large variations in properties are not uncommon (viscosity etc.), therefore, the only logical conclusion to draw is that the sample of polystyrene used for this test has a very low
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molecular weight or is very highly branched. (The small range in temperature over which melting occurs displays that chain lengths of this sample of polystyrene are very similar). This would lead to the transition in question being deemed a melting point. Structure of polystyrene:

Running the sample through a viscometer in an appropriate solvent could verify a low molecular weight. The relative bulk of the phenyl group attached to the polymer also contributes another variable to the material-the tacticity of polystyrene can dictate whether it can pack into a more ordered solid structure with more stable thermal properties. The more ordered the Phenyl groups lie along the chain, the better able they are to pack in an ordered fashion and this case is syndiotactic polystyrene, the structure of which is shown below:

This is obviously more suited to packing than atactic polystyrene (formed by random polymerisation), which has its phenyl groups randomly oriented. PVC: High molecular weight PVC differs from the low molecular weight variety only in terms of chain length and both compounds have the same structure:

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The difference between the two forms is merely in the value of n. The similarity, however, does not end there. The lower temperature regions of the graphs in each case are strikingly similar in shape with glass transitions occurring at, 81.252oC and 85.385oC for low and high molecular weight respectively. This is quite a high value for a glass transition and can be attributed to the Cl- group attached to the main Carbon chain taking a greater share of the electrons in its bond with Carbon. This has the effect of setting up an electric dipole that may interact with the other molecules via a dipoledipole interaction. A second transition is evident in the higher temperature regions of the graph for low density PVC. Starting at 175.75oC with a peak at 187.53oC and an endothermic enthalpy change of 4.950.25J/g, it has far too small an energy to be a melting point and is possibly a degradation temperature. No information was available as regards degradation temperatures, however, so to err on the side of caution, this will be put down to impurities present in the material. An increase in the value of n for a straight chain polymer causes an increase in the length over which a given molecule can interact with its nearest neighbours by the Van der Waals force, thus increasing the temperature at which various transitions occur. Conclusions: Analysis of the polymers was preceded by the analysis of a material with a well-defined melting point and enthalpy of melting (Indium). The result of this measurement compared with the theoretical values as follows: Accepted enthalpy of melting of Indium: 28.5J/g Value obtained through DSC: 21.4451.07J/g. Accepted melting point of Indium: 156.6oC. Value obtained through DSC: 156.9 (onset). These results display two important points. Temperature values for transitions are quite accurate and agree to within a fraction of a percent. However, values given for enthalpy transitions can be taken with a pinch of salt with our value being about 25% out from what can be called acceptable. The following table serves to compare values obtained in this experiment with universally accepted values: Material Indum HDPE TG (oC) TM (oC) Theory Tg n/a n/a 156.9 124.92 -Theory Tm 156 130

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High MW PVC Low MW PVC PAA PMMA Polystyrene PVA

85.385 81.252 -103.32 -90

n/a n/a 130 -71.556 162.18

85 81 106 110 104 85 200

Previous page: Table 2-comparison of values obtained from the experiment versus accepted values.

All errors in enthalpies were specified by the equipment manufacturer at 5% of measured values. Additional excercises: Percentage crystallinity of polyethylene sample:
100% = 293.61J / g

The percentage crystallinity is therefore:

118.3 100 = 40.2 2.1% 293.61

Thermogram of polymer with the following transitions: Endothermic transition at 80oC, Tg at 145oC, Tm of 235oC and a decomposition temperature of 400oC Is shown in figure 3:
Figure 3:

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All other requested information was discussed earlier in this report.

References:
www.fsref.com/Fatal/FEA00002.SHTML www.pslc.ws/mactest/dsc.htm ois.nist.gov/nistpubs/technipubs/ recent/search.cfm?dbibid=12927

irc.nrc-cnrc.gc.ca/ cbd/cbd154e.html
repository.matdl.org/retrieve/ 2961/polymer+final+research+article.pdf

www.chem.ox.ac.uk/.../ Lavender/lavender.html
www.erkol.com/eng/Characteristics.htm

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