# US 5,346,306 A · Method and apparatus for modulated differential analysis

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- Number: US 5,346,306 A
- Document ID: US5346306A
- Status: Granted
- Kind: A
- Application number: 08/060,214
- Filed: 1993-05-07
- Granted: 1994-09-13
- Earliest claimed: 1992-03-02
- Assignees: TA Instruments, Inc.
- Inventors: Michael Reading; Brian K. Hahn; Benjamin S. Crowe
- Web page: https://patentgrep.com/patent/US5346306A

## CPC

- G01N 25/18: by investigating thermal conductivity (by calorimetry G01N25/20; by measuring change of resistance of an electrically-heated body G01N27/18)
- G01N 25/4833: {specially adapted for temperature scanning}
- G01N 25/4866: {by using a differential method}
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)

## Abstract

The present invention relates to differential analytical techniques for determining the composition, phase, structure, identification or other properties of a material that undergoes a transition as function of a driving variable. As applied to differential scanning calorimetric analysis (DSC), the preferred embodiment comprises: (1) heating a sample of the material with a linear temperature ramp that is modulated with a sinusoidal heating rate oscillation; and (2) deconvoluting the resultant heat flow signal into rapidly reversible and non-rapidly reversible components.

## Claims

### Claim 1

A method for analyzing a material using a differential scanning calorimeter comprising the steps of:
(a) selecting an underlying heating rate, modulation frequency and modulation amplitude;
(b) lacing a sample of the material in the differential scanning calorimeter;
(c) varying the temperature of the sample in the differential scanning calorimeter according to the selected underlying heating rate, the selected modulation frequency and the selected modulation amplitude;
(d) recording a signal representative of differential changes in the heat flow to and from the sample; and
(e) deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute at least one deconvoluted signal.

### Claim 2 (depends on 1)

The method of claim 1, wherein the step of deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute at least one deconvoluted signal comprises deconvoluting the signal into rapidly reversible and non-rapidly reversible components.

### Claim 3 (depends on 2)

The method of claim 2, further comprising the step of adjusting the frequency of the modulation of the temperature according to the at least one deconvoluted signal.

### Claim 4 (depends on 2)

The method of claim 2, further comprising the step of adjusting the amplitude of the modulation of the temperature according to the at least one deconvoluted signal.

### Claim 5 (depends on 2)

The method of claim 2, further comprising the step of controlling the underlying heating rate according to the at least one deconvoluted signal.

### Claim 6

A method for analyzing a material using a differential thermal analyzer comprising the steps of:
(a) selecting an underlying heating rate, modulation frequency and modulation amplitude;
(b) placing a sample of the material in a differential thermal analyzer;
(c) varying the temperature of the sample in the differential thermal analyzer according to the selected underlying heating rate, the selected modulation frequency and the selected modulation amplitude;
(d) recording a signal representative of differential changes in the heat flow to and from the sample; and
(e) deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute at least one deconvoluted signal.

### Claim 7 (depends on 6)

The method of claim 6, wherein the step of deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute at least one deconvoluted signal comprises deconvoluting the signal into rapidly reversible and non-rapidly reversible components.

### Claim 8 (depends on 7)

The method of claim 7, further comprising the step of adjusting the frequency of the modulation of the temperature according to the at least one deconvoluted signal.

### Claim 9 (depends on 7)

The method of claim 7, further comprising the step of adjusting the amplitude of the modulation of the temperature according to the at least one deconvoluted signal.

### Claim 10 (depends on 7)

The method of claim 7, further comprising the step of controlling the underlying heating rate according to the at least one deconvoluted signal.

### Claim 11

A differential scanning calorimeter comprising:
(a) means for varying the temperature of a sample in the differential scanning calorimeter according to an underlying heating rate;
(b) means for selecting a modulation frequency and a modulation amplitude;
(c) means for controlling the temperature of the sample according to the selected underlying heating rate, modulation frequency and modulation amplitude;
(d) means for detecting the heat flow to and from the sample with respect to a reference as a function of temperature, as the temperature is varied according to the modulation frequency and the modulation amplitude;
(e) means for recording a signal representative of differential changes in the heat flow to and from the sample; and
(f) means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute at least one deconvoluted signal.

### Claim 12 (depends on 11)

The differential scanning calorimeter of claim 11, wherein the means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute at least one deconvoluted signal comprises means for deconvoluting the signal into rapidly reversible and non-rapidly reversible components.

### Claim 13 (depends on 12)

The differential scanning calorimeter of claim 12, further comprising means for adjusting the frequency of the modulation of the temperature according to the at least one deconvoluted signal.

### Claim 14 (depends on 12)

The differential scanning calorimeter of claim 12, further comprising means for adjusting the amplitude of the modulation of the temperature according to the at least one deconvoluted signal.

### Claim 15 (depends on 12)

The differential scanning calorimeter of claim 12, further comprising means for controlling the underlying heating rate according to the at least one deconvoluted signal.

### Claim 16

A differential thermal analyzer comprising:
(a) means for varying the temperature of a sample in the differential thermal analyzer according to an underlying heating rate;
(b) means for selecting a modulation frequency and a modulation amplitude;
(c) means for controlling the temperature of the sample according to the selected underlying heating rate, modulation frequency and modulation amplitude;
(d) means for detecting the heat flow to and from the sample with respect to a reference as a function of temperature, as the temperature is varied according to the modulation frequency and the modulation amplitude;
(e) means for recording a signal representative of differential changes in the heat flow to and from the sample; and
(f) means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute at least one deconvoluted signal.

### Claim 17 (depends on 16)

The differential thermal analyzer of claim 16, wherein the means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute at least one deconvoluted signal comprises means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample into rapidly reversible and non-rapidly reversible components.

### Claim 18 (depends on 17)

The differential thermal analyzer of claim 17, further comprising means for adjusting the frequency of the modulation of the temperature according to the at least one deconvoluted signal.

### Claim 19 (depends on 17)

The differential thermal analyzer of claim 17, further comprising means for adjusting the amplitude of the modulation of the temperature according to the at least one deconvoluted signal.

### Claim 20 (depends on 17)

The differential thermal analyzer of claim 17, further comprising means for controlling the underlying heating rate according to the at least one deconvoluted signal.

### Claim 21

A method for analyzing a material comprising the steps of:
(a) placing a sample of the material in an apparatus for detecting differential changes in the heat flow to a sample material with respect to a reference, as a function of temperature;
(b) varying the temperature at an underlying heating rate modulated by a modulation function, said modulation function having a preselected modulation frequency and a preselected modulation amplitude;
(c) monitoring a differential signal representative of the differential change in the heat flow to the sample material with respect to the reference;
(d) recording the differential signal representative of the differential change in the heat flow to the sample material with respect to the reference; and
(e) deconvoluting the signal representative of the differential change in the heat flow to the sample material with respect to the reference to compute at least one deconvoluted signal.

### Claim 22 (depends on 21)

The method of claim 21, wherein the step of deconvoluting the signal representative of the differential change in the heat flow to the sample material with respect to the reference to compute at least one deconvoluted signal comprises deconvoluting the signal representative of the differential change in the heat flow to the sample material with respect to the reference, into rapidly reversing, and non-rapidly reversing components.

### Claim 23 (depends on 21)

The method of claim 21, wherein the modulation function is a sinusoidal oscillation.

### Claim 24 (depends on 21)

The method of claim 21, wherein the modulation function is a combination of at least two sinusoidal oscillations.

### Claim 25 (depends on 21)

The method of claim 21, wherein the modulation function is selected from the group of modulation functions consisting of square waves, sawtooth waves, triangular waves, pulse waves, polynomial waves, and combinations thereof.

### Claim 26 (depends on 21)

The method of claim 21, further comprising the step of deconvoluting the signal representative of the differential change in the heat flow to the sample material with respect to the reference, using a discrete Fourier transform.

### Claim 27 (depends on 26)

The method of claim 26, wherein the signal representative of differential changes in the heat flow to and from the sample is differential temperature.

### Claim 28 (depends on 21)

The method of claim 21, wherein the differential signal representative of the differential change in the heat flow to the sample material with respect to the reference, is differential temperature.

### Claim 29

A thermal analysis instrument comprising:
(a) a furnace comprising a heater, a heater controller, and a furnace chamber;
(b) a sample pan and a reference pan in the furnace chamber;
(c) means for monitoring the temperature of the sample pan and the temperature difference between the sample pan and the reference pan;
(d) means for controlling the temperature of the furnace chamber;
(e) means for receiving a signal representative of the temperature of the sample pan and of the temperature difference between the sample pan and the reference pan, for calculating a signal representative of differential changes in heat flow to the sample pan with respect to heat flow to the reference pan from the signal representative of the temperature of the sample pan and of the temperature difference between the sample pan and the reference pan, and for controlling the means for controlling the temperature of the furnace chamber;
(f) means for (i) selecting an underlying heating rate for the furnace chamber, (ii) selecting a modulation frequency and a modulation amplitude, and (iii) controlling the temperature of the sample pan according to the selected underlying heating, modulation frequency and modulation amplitude;
(g) means for recording the signal representative of differential changes in the heat flow to the sample pan with respect to the heat flow to the reference pan; and
(h) means for deconvoluting the signal representative of differential changes in the heat flow to the sample pan with respect to the heat flow to the reference pan to compute at least one deconvoluted signal.

### Claim 30 (depends on 29)

The thermal analysis instrument of claim 29, wherein the means for deconvoluting the signal representative of differential changes in the heat flow to the sample pan with respect to the heat flow to the reference pan to compute at least one deconvoluted signal comprises means for deconvoluting the signal representative of differential changes in the heat flow to the sample pan with respect to the heat flow to the reference pan into rapidly reversible an non-rapidly reversible components.

### Claim 31 (depends on 30)

The thermal analysis instrument of claim 30, wherein the means for deconvoluting the signal representative of differential changes in the heat flow to the sample pan with respect to the heat flow to the reference pan into rapidly reversible and non-rapidly reversible components uses a discrete differential Fourier transform technique.

### Claim 32 (depends on 29)

The thermal analysis instrument of claim 29, wherein the sample pan and the reference pan are on a support in the furnace chamber, and wherein the support serves as the major heat flow path for transferring heat from the furnace to the sample pan and to the reference pan.

### Claim 33

A thermal analysis instrument comprising:
(a) a sample position and a reference position;
(b) means for heating a sample placed at the sample position and a reference placed at the reference position;
(c) means for monitoring the heat flow to the sample and the heat flow to the reference;
(d) means for receiving a signal representative of the heat flow to the sample and the heat flow to the reference;
(e) means for recording the signal representative of the heat flow to the sample and the heat flow to the reference;
(f) means for selecting an underlying heating rate, modulation frequency and modulation amplitude;
(g) means for controlling the temperature of the sample according to the selected underlying heating rate, modulation frequency and modulation amplitude;
(h) means for calculating a signal representative of differential changes in the heat flow to the sample with respect to the heat flow to the reference; and
(i) means for deconvoluting the signal representative of differential changes in the heat flow to the sample with respect to the heat flow to the reference to compute at least one deconvoluted signal.

### Claim 34 (depends on 33)

The thermal analysis instrument of claim 33, wherein the means for deconvoluting the signal representative of differential changes in the heat flow to the sample with respect to the heat flow to the reference to compute at least one deconvoluted signal comprises means for deconvoluting the signal representative of differential changes in the heat flow to the sample with respect to the heat flow to the reference into rapidly reversible and non-rapidly reversible components.

### Claim 35 (depends on 34)

The thermal analysis instrument of claim 34, wherein the means for deconvoluting the signal representative of differential changes in the heat flow to the sample with respect to the heat flow to the reference into rapidly reversible and non-rapidly reversible components uses a discrete differential Fourier transform technique.

### Claim 36 (depends on 33)

The thermal analysis instrument of claim 33, wherein the sample and the reference are on a support, and wherein the support serves as the major heat flow path for heat transfer.

### Claim 37

A method for analyzing a material using a differential scanning calorimeter comprising the steps of:
(a) selecting an underlying heating rate, modulation frequency and modulation amplitude;
(b) placing a sample of the material in the differential scanning calorimeter;
(c) varying the temperature of the sample in the differential scanning calorimeter according to the selected underlying heating rate, the selected modulation frequency and the selected modulation amplitude;
(d) recording a signal representative of differential changes in the heat flow to and from the sample; and
(e) deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute two deconvoluted signals.

### Claim 38 (depends on 37)

The method of claim 37, wherein the step of deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute two deconvoluted signals comprises deconvoluting the signal into a rapidly reversible component and a non-rapidly reversible component.

### Claim 39

A method for analyzing a material using a differential thermal analyzer comprising the steps of:
(a) selecting an underlying heating rate, modulation frequency and modulation amplitude;
(b) placing a sample of the material in a differential thermal analyzer;
(c) varying the temperature of the sample in the differential thermal analyzer according to the selected underlying heating rate, the selected modulation frequency and the selected modulation amplitude;
(d) recording a signal representative of differential changes in the heat flow to and from the sample; and
(e) deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute two deconvoluted signals.

### Claim 40 (depends on 39)

The method of claim 39, wherein the step of deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute two deconvoluted signals comprises deconvoluting the signal into a rapidly reversible component and a non-rapidly reversible component.

### Claim 41

A differential scanning calorimeter comprising:
(a) means for varying the temperature of a sample in the differential scanning calorimeter according to an underlying heating rate;
(b) means for selecting a modulation frequency and a modulation amplitude;
(c) means for controlling the temperature of the sample according to the selected underlying heating rate, modulation frequency and modulation amplitude;
(d) means for detecting the heat flow to and from the sample with respect to a reference as a function of temperature, as the temperature is varied according to the modulation frequency and the modulation amplitude;
(e) means for recording a signal representative of differential changes in the heat flow to and from the sample; and
(f) means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute two deconvoluted signals.

### Claim 42 (depends on 41)

The differential scanning calorimeter of claim 41, wherein the means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute two deconvoluted signals comprises means for deconvoluting the signal into a rapidly reversible component and a non-rapidly reversible component.

### Claim 43

A differential thermal analyzer comprising:
(a) means for varying the temperature of a sample in the differential thermal analyzer according to an underlying heating rate;
(b) means for selecting a modulation frequency and a modulation amplitude;
(c) means for controlling the temperature of the sample according to the selected underlying heating rate, modulation frequency and modulation amplitude;
(d) means for detecting the heat flow to and from the sample with respect to a reference as a function of temperature, as the temperature is varied according to the modulation frequency and the modulation amplitude;
(e) means for recording a signal representative of differential changes in the heat flow to and from the sample; and
(f) means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute two deconvoluted signals.

### Claim 44 (depends on 43)

The differential thermal analyzer of claim 43, wherein the means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample to compute two deconvoluted signals comprises means for deconvoluting the signal representative of differential changes in the heat flow to and from the sample into a rapidly reversible component and a non-rapidly reversible component.