THERMAL ANALYSIS GROUP 6

Hamzah Mukhtar

Vamakshi Khati

Daniel Gmez

Pablo Ramos

12.11.2013

CONTENTS

1-INTRODUCTION..3

2-DSC..4

3-DILATOMETRY...6

4-DMTA..8

5-CONCLUSIONS10

6-REFERENCES..11

1 INTRODUCTION

One customer has a problem with some polymer cable gland that fails after a few months. What is seen is that this polymer has multiple fractures and its surface is a bit harder than reference sample. This polymer cable gland is used in power cables and it fails in Asia region. In this situation what should be determined is first of all what makes a polymer harder, why multiple fractures appear after long time (few months) and what is the difference induced, when choosing Asia region. Problem is related with polymers, so there are some particular aspects to focus on when measuring parameters in order to determine what have happened and why it failed. When dealing with polymers some effects should be taken into account as: Tg Temperature of recrystallization Tm Grade of crystallinity Degradation

In order to guess all questions mentioned before the main measurements used in the report are: DSC Dilatometry DMTA

2 DSC

Differential Scanning Calorimetry is a thermo analytical technique that allows us to measure the amount of energy in terms of heat that is absorbed or released when the sample is heated or cooled, providing data related with endothermic/exothermic reactions and thus, providing information about the processes that are related with them. DSC instrumentation consists in two more or less equal chambers; one chamber contains the reference sample (usually alumina, reference sample must to be inert) where the heat capacitance is well defined in more or less all temperature ranges and in the other chamber is our sample.

The experiment consists on the following: Sample holder is heated uniformly in both chambers (constant heating rate in time), our sample will may experience some changes of phase, or crystallinity grade, etc. so it will absorb or release heat to achieve its new form, the experiment consists on balancing these temperatures in order to make them the same and because of this balance we obtain curves Heat flow VS time/Temperature that will provide a lot of information about the changes in the sample because of the temperature, thus heat flow is measured by comparing the difference in temperature across the sample and the reference. Parameters that have to be measured are the following ones:

There are factors to take into account like the temperature range; it has to be from -120C to 725C, though an inert atmosphere is required above 600C. Al, Cu, Au, Pt, alumina, and graphite are typical sample holders in order to avoid reactions with samples. Atmospheres could be of nitrogen, air, oxygen, argon, vacuum or controlled mixed gases.

The typical curve of a polymer obtained with DSC scan is the following:

In the graph the main points we have to take into acount is that this curves represent some changes in our material and they are showed in endothermic/exothermic reactions (when the curve is shifted

upwards means that it is an endohermic reaction and part of the curve shifted down means that it is an exothermic reaction). As shown in the figure there are quite a lot of reactions in a polymer (glass transition, crystallization, melting, oxidation and degradation), with these graph it is possible to determine really valuable temperatures as Tm, Tg, temperature of recrystallization and the temperature where degradation starts to happen.

3 - DILATOMETRY
It is the thermo-analytical method which is used for the measurement of shrinkage and expansion of the materials under controlled temperature range. The amount of shrinkage or expansion is dependent of material properties or characteristics. By using dilatometry following properties can be measured Thermal expansion and coefficient of thermal expansion Volumetric expansion Influence of additives/raw materials Density change Glass transition temperature (Tg) Dilatometric softening point (Td) Phase transition

The degree of expansion divided by the change in temperature is termed as the materials coefficient of expansion () and it varies with temperature.

= Coefficient of expansion L0=Initial sample length T=Change in temperature l=Change in length

Pushrod dilatometry is a method that is used for determination of dimensional changes versus temperature or time while sample is subjected to a controlled temperature program.

A sample is inserted into a special holder within a movable furnace to perform the dilatometric analysis. The sample is placed directly against the push rod and pushrod transmits the length change to a linear variable displacement transducer. Thermal expansion of polymers is shown in the next figure:

ASTM standards for Dilatometry are D618 Practice for Conditioning Plastics for Testing D883 Terminology Relating to Plastics D4065 Practice for Plastics: Dynamic Mechanical Properties: Determination and Report of Procedures

4 - DYNAMIC MECHANICAL THERMAL ANALYSIS

DMTA or DMA measures the temperature dependent visco-elastic properties along with modulus of elasticity. Strain is measured by applying fluctuating stress and thus complex modulus is determined. This approach can be used to locate the glass transition temperature of the material, as well as to identify transitions corresponding to other molecular motions. DSC has sensitivity problem when it comes to detecting Tg of minor components in a polymer, whereas DMTA measures properties from glassy to rubbery region. Amorphous polymers have different glass transition temperatures, above which the material will have rubbery properties instead of glassy behavior and the stiffness of the material will drop dramatically with an increase in viscosity. At the glass transition, the storage modulus decreases dramatically and the loss modulus reaches a maximum. Temperature-sweeping DMA is often used to characterize the glass transition temperature of a material. In the next figure is shown an schematic diagram of DMTA.

DMA measures the visco-elastic properties by transient or dynamic oscillatory tests. Transient tests include stress relaxation and creep. In dynamic oscillatory test, a sinusoidal stress is applied and sinusoidal strain is measured along with phase difference. For polymers the phase difference is intermediate as in next figure.

The following diagram is a typical DMTA curve for amorphous polymer.

5 - CONCLUSIONS

Using all the techniques mentioned before and with previous knowledge of polymers, some mechanisms of hardening are related with recrystallization process, because it will increase the percentage of crystallinity of the polymer and thus it will get harder, getting harder always (or almost always) is related with brittleness and joined to stresses could lead to failure. Also introducing oxygen and carbon atoms in the main chain will lead to hardening, besides CC bonds, oxygen atoms are introduced generating a dipole. The link will be reinforced so there will be an increase in resistance to being deformed, so atmospheric conditions should also be taken into account. In Asia region these glands used for power cables are made of polymers with high content in halogens (for instance PVC can reach 57% of chloride), this is also a problem because it could lead to degradation of the polymer easily. Degradation can occur as a result of the formation and then breakage of double bonds (for instance when a Carbon is bond with a halogen and it breaks). This occurs in PVC in the presence of an acid species. Active Hydrogen atoms will remove a Chlorine atom from the polymer molecule, forming Hydrochloric acid (HCl) causing dechlorination of adjacent Carbon atoms. These dechlorinated Carbon atoms tend to form double bonds which can be broken in an ozone atmosphere (normal conditions). Conclusions are related then to avoid recrystallization (be aware of Tg and temperature of recrystallization of the polymer), take into account atmosphere conditions and content of halogens in the polymer used.

10

5 REFERENCES

Notes of Thermal Analysis, course given in TUT. http://www.mate.tue.nl/mate/pdfs/10367.pdf http://www.files.chem.vt.edu/chem-dept/marand/Lecture23.pdf http://en.wikipedia.org/wiki/Polyvinyl_chloride http://www4.ncsu.edu/~lalucia/courses/WPS-595B-BIOMATERIALSCHARACTERIZATION/DSC.pdf http://meteo-tech.co.il/e-Catalog/pdf/DIL.pdf http://www.sealseastern.com/PDF/DynamicMechThermalAnal.pdf http://www.perkinelmer.com/CMSResources/Images/44-74546GDE_IntroductionToDMA.pdf https://www.google.es/search?q=DSC+curves&espv=210&es_sm=122&tbm=isch&tbo=u&sourc e=univ&sa=X&ei=FgmFUv6lMsOM4ASG54HgDA&ved=0CDQQsAQ&biw=1241&bih=550 http://www.hitachi-hitecscience.com/en/documents/technology/thermal_analysis/application_TA_065e.pdf http://science.fire.ustc.edu.cn/download/download1/book%5Cchemistry%20engineering%5CTh ermal_Analysis_Fundamentals_and_Applications_to_Polymer_Science%5CThermal_Analysis_Fu ndamentals_and_Applications_to_Polymer_Science.pdf

11