Calisto Calibration Procedure

CONTENTS
Introduction Calibration Temperature Correction Method Temperature Correction Processing Sensitivity Coefficient Enthalpy Calibration Sensitivity Coefficient Joule Effect Calibration 1 2 3 5 7

Introduction Calibration To calibrate using heat of fusion standards, it is necessary to know; (1) the melting temperature, (2) the Enthalpy. The Calisto software allows the user to generate a temperature correction coefficient based on known melts of certain standards and a sensitivity coefficient to convert the heat flow in terms of energy. Heat of Fusion Standard Naphthalene Indium Tin Lead Zinc Aluminum Silver Gold Melt (C) 80.23 156.59 231.94 327.47 419.56 660.33 961.78 1064.18 Enthalpy (J/g) 147.6 28.5 60.2 23.0 107.4 401.3 104.8 64.5

Above is a list of just some popular standards used in calibrating your apparatus. For Calvet designed sensors; such as the SenSys or C80 (3 dimensional sensor), the sensitivity coefficient is generated by performing a Joule Effect calibration. Any new or repaired sensor will be accompanied by a sensitivity coefficient data-sheet, performed at our factory before delivery.

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Calisto Calibration Procedure

Temperature Correction Method When writing your experimental method to perform a melting of a standard, it is recommended to perform a pre-melting first, then cool and use the second heating to analyze the value of Tonset.

Also in your method, make sure that no previously stored temperature correction is being used; otherwise you will be performing a correction of a correction.

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Calisto Calibration Procedure

Temperature Correction Processing Use the data-file to integrate the results, which will obtain the onset point for the melting.

For temperature calibration, the onset point is where the tangent of the initial slopes maxima is projected back to the baseline; this intersect is taken as Tonset and is regarded as the melting point of the standard.

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Calisto Calibration Procedure

In the Processing application, under the menu-bar heading Maths, select the item Temperature correction to obtain the table below.

This can be populated with the results from the onset point of each heat-of-fusion experiment. Note: Each standard can be run twice; once at a low heating and repeated at a faster heating, thus producing two data sets per sample. It is recommended to produce at least five data-sets to obtain a relatively accurate polynomial.

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Sensitivity Coefficient Enthalpy Calibration For non-Calvet type sensors, the Enthalpy calibration is performed by generating a sensitivity coefficient. Again, use a standard to perform a heat-of-fusion experiment. If the intension is to recalibrate the sensitivity coefficient, then any existing coefficient must be set to zero. When viewing the heat flow data, it is considered that the peak Area of the endothermic effect will be equal to the Enthalpy, measured here in, V.s/mg.

Typically, Enthalpy is expressed in, J/g, so in order to calibrate each heat-flow sensor, SETARAM allows the user to generate a Sensitivity coefficient, which has the following relationship: Sensitivity = Area = [V.s/mg] = mV.s Enthalpy [J/g] J Also, the Joule can be expressed as the Watt-Second; J Thus, Sensitivity = mV = W V mW = W.s

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Calisto Calibration Procedure

Therefore, once the sensitivity coefficients are determined, the value of Heat Flow is expressed in units of Power, (mW). The sensitivity coefficient is generated by populating a Regression table. For the temperature column, enter the Tonset value for each melting. It is recommend to do as many different standards as possible to ensure the whole temperature range is calibrated in terms of Enthalpy. Again, in the Processing application, under the menu-bar heading Maths, select the item Regression to obtain the table below.

TIP:- A preview of the regression is available for viewing. As a general rule the sensitivity coefficient is parabolic in shape: Avoid choosing too high an order of polynomial that may attempt to do a best-fit sinusoid, this would be wrong.

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Calisto Calibration Procedure

Sensitivity Coefficient Joule Effect Calibration The Joule Effect principle is where the transformation of electrical energy is made into heat. To be more precise, an electrical current, I, flowing through a conductor of resistance, R, during a time, t, generates a heat quantity, Q=RI2 t. The Calvet principle uses this heat quantity in the apparatus to generate a proportional difference when a change in heat-flow occurs between a sample and reference chamber within the same furnace. With older versions of software, the joule effect calibration was activated by a dongle and gave an extra zone in the acquisition software. Note: The Joule Effect Zone will automatically set the sensitivity coefficients to zero.

With SetSoft (16bit) the EJ calibration option has to be added via a floppy disk and is a separate application module. In this case the EJ3 and software has to be started manually. When using Calisto the EJ3 can also be started manually, but it is designed to be connected to an additional serial port (or USB) for automated software control. The principle of the EJ3 is to produce an exact measure of power (mW) into the senor. Heat Capacity is defined by the ratio of heat quantity exchanged by the system with the surrounds during a temperature change. Page 7 of 8

Calisto Calibration Procedure

The Calvet configuration of the thermopile element is to detect heat flow between a reference and sample by electrically balancing two thermopiles that will produce a voltage difference if any heat flow is detected. This is a direct measure of heat quantity (Q). Q is equivalent to [J.K-1] The Heat Quantity, Q, will also be proportional to the mass, m, of the sample and its specific heat capacity, Cp, for a change in temperature, T, over time, t. Hence, dQ = m.Cp dT dt dt Or, Q = m.Cp

For a single thermocouple type DSC, Heat Flow [mW], has to be established from a known mass of sample with a known specific heat capacity in order to calibrate the Heat Flow measurement. Generally, Specific Heat Capacity is the energy that raises the temperature of one kilogram by one kelvin; expressed by: Cp = J.Kg-1.K-1 The Energy is thus calculated from: J = Cp.Kg.K In the case of the Calvet principle, Power is already given by the Joule Effect calibration. So, (W) = J.s-1 (Heat Flow measured in milliWatts)

After using the Joule Effect calibration a set of sensitivity coefficients are generated that follow the form: S(T)= A0 + A1.T + A2.T2 + A3.T3 + A4.T4 with units of V/mW. This equation converts the raw heat-flow signal (V) to power (mW) at that given temperature.

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