Thermal analysis equipment and control software for thermal analysis equipment

Abstract

To provide a thermal analysis device and control software for the thermal analysis device with which it is possible to analyze the change of states of a sample in detail, while grasping and associating a change of colors of the sample in detail due to a temperature change of the sample.SOLUTION: Provided is a thermal analysis device for measuring and calculating the physical properties of a sample while changing the temperature of the sample by heating or cooling so as to acquire thermal analysis data and capturing the image of the sample so as to acquire image data. The thermal analysis device comprises: means for displaying a graph about related to the temperature or time of the thermal analysis data; means for displaying a sample image of the image data; means for generating color information data in the range, and of the type, selected from the sample image; means for displaying graphs related to the temperature or time of the color information data side by side, without being superimposed on graphs related to the temperature or time of the thermal analysis data; and means for displaying a marker at a discretionary point in one of the graphs, and showing a marker at a point in the other of the graphs, the measurement time of which is synchronous with the point where the marker is shown.SELECTED DRAWING: Figure 14

Description

[Technical Field]

[0001] The present invention relates to a thermal analysis instrument, particularly to a sample observation type thermal analysis instrument and its control software. [Background technology]

[0002] Thermal analysis is defined as "a set of techniques for measuring certain physical properties of a substance (including its reaction products) as a function of temperature or time while the temperature of the substance is changed according to a certain program." Thermal analysis includes various techniques depending on the type of sample and the purpose of the measurement, such as thermogravimetry (TG), which measures the change in mass of a sample while changing the temperature by heating or cooling the sample, differential thermal analysis (DTA), which measures the temperature difference between the sample and a reference material, differential scanning calorimetry (DSC), which measures the heat flow difference between the sample and a reference material, and thermomechanical analysis (TMA), which measures the dimensional change of a sample.

[0003] Patent Document 1 discloses a thermal analysis device for measuring the thermal behavior of a sample in a heating furnace as the temperature changes. The heating furnace is provided with an opening for observing the sample, and an imaging device is provided for capturing image data of the sample through the opening. This thermal analysis device displays color information generated from the image data, superimposed on the temperature, along with the thermal behavior of the sample as the temperature changes. Specifically, a graph of TG data and graphs of R, G, and B values ​​are displayed superimposed on each other, with temperature as the horizontal axis.

[0004] Among thermal analyzers, DSC and DTA typically measure data during the temperature increase and decrease process, displaying graphs of the temperature increase and decrease, one above the other, with temperature on the horizontal axis. For example, because the baseline of DSC data depends on the heat capacity of the sample, the graph of the temperature increase shifts downward and the graph of the temperature decrease shifts upward, so the two graphs do not overlap. However, when the thermal analyzer of Patent Document 1 displays the DSC data and color information such as RGB values ​​superimposed on the horizontal axis of temperature, the graph of the color information during the temperature increase and the graph of the color information during the temperature decrease overlap, which can make analysis or visualization difficult. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-1870 Summary of the Invention [Problem to be solved by the invention]

[0006] One object of the present invention is to provide a thermal analysis device and control software for the thermal analysis device that can analyze changes in the state of a sample in detail while closely understanding and correlating changes in the color of the sample that accompany changes in the temperature of the sample. [Means for solving the problem]

[0007] One aspect of the present invention is a thermal analysis apparatus that measures and calculates the physical properties of a sample while changing the temperature of the sample by heating or cooling the sample to obtain thermal analysis data, and also photographs the sample to obtain image data, and includes: a thermal analysis graph display means that displays a graph of the thermal analysis data related to temperature or time on a display device; a sample image display means that displays a sample image of the image data on the display device; a color information generation means that generates color information data of a range and type selected from the sample image; a color information graph display means that displays the graph of the color information data related to temperature or time on the display device side by side with the graph of the thermal analysis data related to temperature or time without superimposing it on the graph; and a marker display means that displays a marker at an arbitrary point on one of the graphs, and also displays markers on other points on the graph whose measurement time is synchronized with the point where the marker is displayed. The thermal analysis graph display means and the color information graph display means display one of the thermal analysis data and the color information data as a graph related to temperature and the other as a graph related to time, and the marker display means displays the markers individually and identifiably at points on each graph where measurement times are synchronized. It is characterized by:

[0008] In another aspect of the present invention, a thermal analysis apparatus measures and calculates the physical properties of a sample while changing the temperature of the sample by heating or cooling the sample to obtain thermal analysis data, and also photographs the sample to obtain image data, comprises: a thermal analysis graph display means for displaying a graph of the thermal analysis data related to temperature or time on a display device; a sample image display means for displaying a sample image of the image data on the display device; a color information generation means for generating color information data of a range and type selected from the sample image; a color information graph display means for displaying the graph of the color information data related to temperature or time on the display device side by side without superimposing it on the graph of the thermal analysis data related to temperature or time; and a marker display means for displaying a marker at an arbitrary point on one of the graphs, and also displaying markers on other points on the graph whose measurement time is synchronized with the point where the marker is displayed, wherein the thermal analysis graph display means displays a graph of the thermal analysis data related to temperature in which there are multiple thermal analysis data values ​​corresponding to the same temperature as the temperature of the sample increases and decreases, and the marker display means displays each of the markers individually and identifiable at points on the thermal analysis data graph and the color information data graph whose measurement time is synchronized.

[0009] In the thermal analysis apparatus of the present invention, the marker display means may be configured to move markers displayed on other graphs in response to movement of a marker displayed on one graph.In the thermal analysis apparatus of the present invention, the marker display means may move a marker displayed on the graph in response to a value within a predetermined temperature range or time range being selected using a slider bar. In the thermal analysis instrument of the present invention, the color information generating means may be capable of selecting a plurality of ranges for generating color information data from the sample image.

[0010] In yet another aspect of the present invention, there is provided control software for a thermal analysis apparatus which causes a computer for controlling a thermal analysis apparatus which measures and calculates the physical properties of a sample while changing the temperature of the sample by heating or cooling the sample to obtain thermal analysis data, and which photographs the sample to obtain image data, to function as: thermal analysis graph display means for displaying a graph of the thermal analysis data relative to temperature or time on a display device; sample image display means for displaying a sample image of the image data on the display device; color information generation means for generating color information data of a range and type selected from the sample image; color information graph display means for displaying a graph of the color information data relative to temperature or time side by side with the graph of the thermal analysis data relative to temperature or time without superimposing it on the graph; and marker display means for displaying a marker at an arbitrary point on one of the graphs, and also displaying markers on other graphs whose measurement times are synchronized with the points where the marker is displayed, wherein the thermal analysis graph display means and the color information graph display means display one of the thermal analysis data and the color information data as a graph relative to temperature and the other as a graph relative to time, and the marker display means displays each of the markers individually and identifiable at points on each graph whose measurement times are synchronized.

[0011] In still another aspect of the present invention, a computer controls a thermal analysis apparatus that measures and calculates the physical properties of a sample while changing the temperature of the sample by heating or cooling the sample to obtain thermal analysis data, and also photographs the sample to obtain image data; the computer serves as thermal analysis graph display means for displaying a graph relating to temperature or time of the thermal analysis data on a display device, as sample image display means for displaying a sample image of the image data on the display device, and as color information generation means for generating color information data of a range and type selected from the sample image, by arranging the graph relating to temperature or time of the color information data on the graph relating to temperature or time of the thermal analysis data without superimposing it on the graph relating to temperature or time of the thermal analysis data, and by displaying the graph. Control software for a thermal analysis apparatus that functions as a color information graph display means to be displayed on the apparatus, and as a marker display means that displays a marker at any point on one of the graphs and also displays markers at other points on the graph whose measurement time is synchronized with the point where the marker is displayed, wherein the thermal analysis graph display means displays a graph related to the temperature of the thermal analysis data in which there are multiple thermal analysis data values ​​corresponding to the same temperature as the temperature of the sample rises and falls, and the marker display means displays each of the markers individually and identifiably at points on the thermal analysis data graph and the color information data graph whose measurement time is synchronized.

[0012] The present invention is not limited to the above objects or aspects. Further details, features, functions and / or advantages of the present invention will become more apparent from the following description of preferred exemplary embodiments of the present invention. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is an explanatory diagram showing the overall configuration of a thermal analysis device according to one embodiment of the present invention; [Figure 2] 1 is a cutaway perspective view showing the structure of the periphery of a heating furnace of a thermal analysis apparatus according to one embodiment of the present invention, in which hatching that should be applied to cross-sectional portions has been partially omitted. [Figure 3] 1 is a block diagram showing a control and processing system of a thermal analysis apparatus according to an embodiment of the present invention. [Figure 4] FIG. 1 is a diagram showing an example of a flowchart for acquiring thermal analysis data and image data by a thermal analysis apparatus according to an embodiment of the present invention. [Figure 5] FIG. 1 is a diagram showing an example of a flowchart for displaying thermal analysis data, image data, etc., on a graph or the like by a thermal analysis apparatus according to an embodiment of the present invention. [Figure 6] FIG. 1 is a diagram showing a graph of thermal analysis data (DSC data) displayed by a thermal analysis device according to one embodiment of the present invention, and a sample image at a desired point on the graph. [Figure 7] FIG. 10 is a diagram showing a screen for selecting a range for generating color information data from a sample image by a color information generating means according to one embodiment of the present invention. [Figure 8]FIG. 2 is a diagram showing color information data generated by a color information generating means according to an embodiment of the present invention. [Figure 9] FIG. 2 is a diagram showing a color information graph displayed by a color information graph display means according to one embodiment of the present invention. [Figure 10] 1 is a diagram showing an example of a graph of thermal analysis data displayed by a thermal analysis apparatus according to one embodiment of the present invention, a sample image at a desired point on the graph, and a graph of color information data. FIG. [Figure 11] FIG. 10 is a diagram showing an example of a marker and a slider bar displayed by a marker display unit according to an embodiment of the present invention. [Figure 12] FIG. 10 is a diagram showing Comparative Example 1 in which a graph of DSC data and a graph of color information data are displayed superimposed with the horizontal axis representing time. [Figure 13] FIG. 10 is a diagram showing Comparative Example 2 in which a graph of DSC data and a graph of color information data are displayed superimposed with the horizontal axis representing temperature. [Figure 14] FIG. 2 is a diagram showing a graph of DSC data and a graph of color information data displayed by a thermal analysis instrument according to one embodiment of the present invention. [Figure 15] FIG. 10 is a diagram showing an example of a color generated from color information data by a gradation generating means. [Figure 16] FIG. 11 is a diagram showing an example in which color gradation is displayed below the graph shown in FIG. 10 without being superimposed thereon. [Figure 17] FIG. 10 is a diagram showing a screen for selecting a plurality of ranges for generating color information data from a sample image by a color information generating means according to another embodiment of the present invention. [Figure 18] FIG. 10 is a diagram showing a graph of DSC data displayed by a thermal analysis apparatus according to another embodiment of the present invention, and a graph of color information data at a plurality of locations on a sample. DETAILED DESCRIPTION OF THE INVENTION

[0014] Example 1 As an embodiment of the thermal analysis apparatus of the present invention, a sample observation type differential scanning calorimetry (DSC) apparatus will be described. Referring to Fig. 1, the thermal analysis apparatus 1 includes a differential scanning calorimetry (DSC) apparatus 2, an automatic sample changer 3, a cooling unit 4, a cover 5 with an observation window, a camera 6, a camera movement mechanism 7, a computer 8, an input device 9, and a display device 10. The computer 8 has installed therein thermal analysis apparatus control software 30, which will be described later.

[0015] Referring to FIG. 2, the DSC apparatus 2 includes a cylindrical case 11 and a heating furnace 14 surrounded by heat insulating materials 12 and 13 on the sides and bottom. The heating furnace 14 includes a measurement chamber 15 with an open top and a thermosensitive plate 16 provided inside the measurement chamber 15. A sample container 17 containing a sample is placed at a predetermined sample measurement position on the thermosensitive plate 16. A sample container 18 containing a reference material is placed at a predetermined reference material measurement position on the thermosensitive plate 16. A heater 14a (see FIG. 3), which generates heat when electricity is applied, is provided inside the side wall of the heating furnace 14. The heating furnace 14 heats the sample and reference material in the measurement chamber 15 by the heat generated by the heater.

[0016] 3, a sample temperature detection means 19 such as a thermocouple is provided at a predetermined sample measurement position on the thermal plate 16, and detects the temperature by contacting or being close to the bottom of a sample container 17 placed at that position. A reference temperature detection means 20 such as a thermocouple is provided at a predetermined reference measurement position on the thermal plate 16, and detects the temperature by contacting or being close to the bottom of a sample container 18 placed at that position. A furnace temperature detection means 21 such as a thermocouple is provided at the bottom of the measurement chamber 15 of the heating furnace 14, and detects the temperature of the heating furnace 14. The DSC apparatus 2 stores the temperatures detected by the sample temperature detection means 19, reference temperature detection means 20, and furnace temperature detection means 21 as a sample temperature signal, reference temperature signal, and furnace temperature signal, respectively, in a memory unit (not shown) provided within the DSC apparatus 2, and transmits them to the computer 8 via wireless or wired communication.

[0017] 2 and 3, a refrigerant jacket 22 connected to the cooling unit 4 by two conduits is installed around the outer periphery of the heating furnace 14. The cooling unit 4 cools the heating furnace 14 and the sample and reference material in the measurement chamber 15 by circulating a cooling medium such as liquid nitrogen between the inside of the refrigerant jacket 22 and the cooling unit 4.

[0018] A lid body 5 with an observation window is attached to the case lid 23 that closes the top of the case 11. The lid body 5 with an observation window includes an inner lid 24 with an observation window that is detachably attached to the heating furnace 14 so as to open and close the top opening of the measurement chamber 15, an intermediate lid 25 with an observation window that is detachably attached to a spacer 5a installed on the case lid 23, and an outer lid 26 with an observation window that is detachably attached to the lid body 5. The reason there are three lids with observation windows is to prevent condensation from forming on the observation windows when cooling with the cooling unit 4, etc. When performing measurement, all of the lids 24, 25, and 26 with observation windows are attached to the lid body 5, and the top opening of the measurement chamber 15 is closed.

[0019] The DSC instrument 2 is a heat flux-type differential scanning calorimeter. Differential scanning calorimetry (DSC) is a method for quantitatively measuring the endothermic and exothermic changes of a sample by applying a constant amount of heat to both the reference and sample. The reference is made of a thermally stable material and does not undergo changes in its physical properties, such as melting or evaporation, even with temperature changes. In contrast, when the sample undergoes an endothermic or exothermic reaction in response to a temperature change according to its own characteristics, its temperature stops changing during the reaction, resulting in a temperature difference ΔT between the sample and the reference. A heat flow to reduce this temperature difference ΔT flows into the sample through the thermal plate 16. The amount of heat flowing into the sample per unit time (heat flow) is proportional to the temperature difference ΔT between the sample and the reference. Therefore, the heat quantity (energy) of the sample can be calculated by integrating the temperature difference ΔT over time, correcting it for temperature dependence, and dividing it by the instrument constant k. In this way, the heat flux flowing into the sample, and therefore the amount of heat, is calculated based on the temperature difference between the sample and the reference. The calorific value obtained by calculation is thermal analysis data (DSC data) obtained by differential scanning calorimetry (DSC) of the sample.

[0020] 1 to 3, camera 6 photographs the sample in sample container 17 placed at a predetermined sample measurement position in measurement chamber 15 through the observation windows of three observation-window-equipped lids 24, 25, and 26 of lid body 5. Image data of the sample photographed by camera 6 is stored in a memory unit (not shown) provided in camera 6 or camera movement mechanism 7, and is also transmitted to computer 8.

[0021] The camera moving mechanism 7 adjusts the position at which the camera 6 photographs the sample. When the observation window covers 24, 25, and 26 are removed from the cover body 5 and a sample or reference substance is installed or replaced in the measurement chamber 15, the camera 6, which is supported by the camera moving mechanism 7 on a horizontal axis, rotates upward and backward and retreats from the vicinity of the cover body 5.

[0022] The automatic sample changer 3 operates when the camera 6, which is pivotally supported by the camera moving mechanism 7, has rotated upward and backward and is retracted, and the observation window covers 24, 25, and 26 have been removed from the cover body 5. The automatic sample changer 3 can place a sample container 17 containing a sample at a predetermined sample measurement position or remove it from that position to the outside through the top opening of the measurement chamber 15. The automatic sample changer 3 may also be configured to place a sample container 18 containing a reference material at a predetermined reference material measurement position or remove it from that position to the outside.

[0023] 3, a computer 8 is installed with thermal analysis apparatus control software 30, which is one embodiment of the present invention. The computer 8 includes a central processing unit (CPU) 27, a graphics processing unit (GPU) 28, a storage device 29 such as an HDD or SSD, etc. The computer 8 transmits and receives various signals to and from the DSC apparatus 2, automatic sample changer 3, cooling unit 4, camera 6, camera movement mechanism 7, input device 9, and display device 10 via wired or wireless communication.

[0024] The input device 9 is a device with which an operator inputs sample measurement conditions, operating instructions for each device, etc. into the computer 8. The input device 9 comprises a keyboard, a mouse, etc., but may also include a touch panel or voice input means.

[0025] The display device 10 displays various information under the control of software 30 installed in the computer 8 and in accordance with input from the input device 9. The display device 10 is formed of a liquid crystal monitor or the like.

[0026] The thermal analysis device 1 is controlled by a computer 8 having software 30 installed, and while heating the sample in a heating furnace 14 or cooling it in a cooling unit 4 to change the temperature of the sample in a measurement chamber 15, it measures and calculates the physical properties of the sample to obtain thermal analysis data, and also photographs the sample with a camera 6 to obtain image data.

[0027] The computer 8 having the software 30 installed therein has the configuration and function of a thermal analysis graph display means 31 that displays a graph of the thermal analysis data relating to temperature or time on the display device 10 .

[0028] The computer 8 in which the software 30 is installed has the configuration and function of a sample image display means 32 that displays a sample image of the image data on the display device 10 .

[0029] The computer 8 in which the software 30 is installed has the configuration and function of a color information generating means 33 that generates color information data of a selected range and type from the sample image.

[0030] The computer 8 having the software 30 installed therein has the configuration and function of a color information graph display means 34 that displays a graph of the color information data relating to temperature or time on the display device 10, side by side with the graph of the thermal analysis data relating to temperature or time without superimposing it on the graph.

[0031] The computer 8 having the software 30 installed therein has the configuration and function of a marker display means 35 that displays a marker at any point on one of the graphs and also displays markers at other points on the graph whose measurement times are synchronized with the point at which the marker is displayed.

[0032] An example of a flowchart for acquiring thermal analysis data and image data of a sample using a thermal analysis apparatus according to an embodiment of the present invention will be described with reference to FIG.

[0033] In step S101, a setting screen for the measurement conditions and temperature program of the thermal analyzer 1 is opened, and the sample name, sample weight, set temperature range, measurement time, measurement interval, etc. are input and set into the computer 8 by the input means 9.

[0034] In step S102, a setting screen for sample imaging conditions of the thermal analysis device 1 is opened, and imaging time, imaging intervals, etc. are input and set into the computer 8 by the input means 9.

[0035] In step S103, measurement is started, and the temperature is controlled by the computer 8 on which the software 30 is installed in accordance with predetermined measurement conditions and a predetermined temperature program, and the heater of the heating furnace 14 is energized to generate heat, heating the sample placed in the sample container 17 placed at the predetermined sample measurement position in the measurement chamber 15, or the cooling unit 4 circulates a cooling medium through two conduits between the inside of the refrigerant jacket 22 and the heating furnace 14, and the sample placed in the sample container 17 placed at the predetermined sample measurement position in the measurement chamber 15. Then, the sample temperature detection means 19 measures the temperature of the sample, and the reference temperature detection means 20 measures the temperature of the reference material, according to predetermined measurement conditions such as the measurement interval.

[0036] In step S104, the computer 8 calculates the heat flux flowing into the sample, ie, the amount of heat, based on the temperature difference between the measured sample temperature and the reference material temperature, and obtains thermal analysis data (DSC data) of the sample.

[0037] In step S201, under the control of a computer 8 having software 30 installed, the camera 6 of the thermal analysis device 1 photographs the sample placed in a sample container 17 placed at a predetermined sample measurement position in the measurement chamber 15 during measurement, in accordance with predetermined sample photography conditions.

[0038] In step S202, the computer 8 acquires image data of the sample being measured.

[0039] In step S105, the thermal analysis data of the sample and the image data of the sample acquired by the computer 8 are stored in the storage device 29 of the computer 8.

[0040] Next, an example of a flowchart for displaying thermal analysis data, image data, etc. in a graph or the like using a thermal analysis apparatus according to one embodiment of the present invention in order to analyze changes in state of a sample accompanying temperature changes will be described.

[0041] 5, in step S301, the thermal analysis apparatus 1 is controlled by the computer 8 having the software 30 installed, and while changing the temperature of the sample in the measurement chamber 15 by heating the sample with the heating furnace 14 or cooling the sample with the cooling unit 4, measures and calculates the physical properties of the sample to obtain thermal analysis data, and also photographs the sample during measurement with the camera 6 to obtain image data. For example, the thermal analysis data and image data can be obtained by measuring and photographing the sample according to the flowchart shown in FIG. 4. Alternatively, the thermal analysis data and image data may be obtained by reading out data stored in the storage device 29 of the computer 8.

[0042] 6 shows an example of a graph of DSC data obtained by measuring the temperature of a sample and the temperature of a reference material while the temperature of the sample is increased to 80°C and then decreased to -50°C, and calculating the temperature difference between the sample and the reference material. Specifically, the thermal analysis graph display means 31 displays a graph of the sample temperature versus time, with the horizontal axis representing time (in minutes) and the vertical axis representing temperature (in degrees Celsius). Also, a graph of the heat flux versus time is displayed, with the horizontal axis representing time (in minutes) and the vertical axis representing heat flux (in mW).

[0043] 6, a sample image of an arbitrarily selected point on a graph of thermal analysis data (DSC data) relating to heat flux and time is displayed by the sample image display means 32. The sample image display means 32 can select multiple points on the graph of thermal analysis data, or select multiple sample images from image data stored in the storage device 29, and display multiple sample images on the display device 10.

[0044] Referring to FIG. 5, in step S302, the color information generating means 33 can select the range and type of color information to be generated from the sample image. FIG. 7 shows an example of a sample observation color information window opened by the color information generating means 33 for selecting the range and type of color information to be generated from the sample image. The sample image is displayed in the sample observation color information window by the sample image display means 32. The sample observation color information window in FIG. 7 has a check box for selecting whether to "select with a square" or "select with a circle" as the range (target range) of color information to be generated from the sample image. In FIG. 7, "select with a circle" is checked, so a dashed circle is displayed in the sample image displayed in the sample observation color information window. The size and position of the target range displayed as a dashed circle can be changed using the input device 9, such as a keyboard or mouse.

[0045] Although not shown in Figure 7, there is also a sample observation color information window for selecting the type of color information to be generated. Color information is information that quantifies the colors of the image data captured by the camera 6. The types of color information to be generated can be selected from "RGB," which expresses colors using a combination of red, green, and blue, which are considered the "three primary colors of light," "CMYK," which expresses colors using a combination of cyan, magenta, and yellow, which are considered the three primary colors of color, and black, "CIE Lab," defined by the International Commission on Illumination (CIE), and "HSV," which expresses colors using a combination of hue, saturation, and value.

[0046] Referring to Fig. 5, in step S303, the color information generating means 33 generates color information data of the range and type selected from the sample image. Referring to Fig. 7, when "Generate" displayed in the sample observation color information window is clicked with the mouse, the color information generating means 33 confirms the selection of the range and type of color information to be generated and generates color information data. Fig. 8 shows an example of color information data generated by the color information generating means 33 in a table. As shown in Fig. 8, the thermal analysis data (Temperature, DSC), image data (observation image), and color information data (R value, G value, B value, etc.) are saved in association with the measurement time (Time).

[0047] FIG. 9 shows graphs of the R, G, and B values, which are the color information data shown in the table of FIG. 8, with time plotted on the horizontal axis. These color information graphs reveal that the color information changes significantly between 5 and 7 minutes and between 14 and 20 minutes (particularly around 19 minutes) after the start of measurement. Thus, the color information graphs allow accurate understanding of the timing and amount of color change in the sample. However, the color information graphs of FIG. 9 do not allow visual understanding of the sample color or its change. Furthermore, the relationship with sample temperature cannot be understood.

[0048] 5, in step S304, the thermal analysis graph display means 31 displays a graph of the thermal analysis data related to temperature or time on the display device 10. Furthermore, the color information graph display means 35 displays the graph of the color information data related to temperature or time on the display device 10 side by side with the graph of the thermal analysis data related to temperature or time without superimposing it on the graph.

[0049] Referring to FIG. 5, in step S305, the marker display means 36 selects an arbitrary point on one graph and displays a marker at the selected point, and also displays markers at points on other graphs whose measurement times are synchronized with the point at which the marker is displayed.

[0050] By displaying the thermal analysis data graph and the color information data graph side by side without overlapping, each graph is easy to see and analyze. Furthermore, by displaying markers at corresponding points on the thermal analysis data graph and the color information data graph, the correspondence between the thermal analysis data and the color information data can be easily understood. Therefore, by analyzing each graph, the state change of the sample due to temperature change can be evaluated in detail.

[0051] For example, Fig. 10 shows a graph of thermal analysis data (DSC data) measured by thermal analysis device 1 when a piece of paper with writing in erasable ballpoint pen was placed in a sample container, heated to 80°C at 10°C / min in an N2 atmosphere, and then cooled to -50°C, with time (measurement time) on the horizontal axis. A graph (Temp) showing the relationship between time (measurement time) and sample temperature is also displayed.

[0052] Figure 10 shows a graph of thermal analysis data (DSC data) along with sample images at five points on the graph. Displaying sample images allows one to grasp the actual color of the sample, but there is a limit to the number of sample images that can be displayed, making it difficult to evaluate local color changes on the sample or to compare and evaluate color changes at multiple locations.

[0053] In Figure 10, a graph of color information data (RGB values) generated from the text portion near the center of the sample image is displayed alongside the thermal analysis data (DSC data) graph, with the horizontal axis representing time from the start of measurement and the scale adjusted to match. The graph of color information data (RGB values) is displayed below the thermal analysis data (DSC data) graph without overlapping, making it possible to understand the timing and amount of color change. Because the thermal analysis data graph and the color information data graph are displayed side by side without overlapping, each graph is easy to see and analyze.

[0054] In Figure 10, circle markers are displayed at points on the two thermal analysis data graphs and the three color information data graphs that correspond to 4 minutes of time (measurement time). Markers are displayed at corresponding points on each graph, making it easy to understand the correspondence between the thermal analysis data and the color information data. For example, it is possible to understand that the sample temperature at a point marked on the color information data graph corresponds to the sample temperature marked on the thermal analysis data sample temperature graph. Displaying the thermal analysis data (DSC data) graph and the color information data graph side-by-side without overlapping makes the thermal analysis data graph and the color information data graph easy to view and analyze. Displaying markers at corresponding points on each graph allows detailed understanding and correlation of the sample color changes associated with temperature changes, enabling detailed analysis of changes in the sample's state. Furthermore, to facilitate adjustment of the marker positions, values ​​on the vertical axis (intensity of color information data) and the horizontal axis (time, temperature, etc.) may be displayed near the markers.

[0055] Furthermore, the marker display means 36 may have a configuration and function that allows markers displayed on other graphs to be moved in response to the movement of a marker displayed on one graph. For example, in FIG. 10, the marker display means 36 may have a configuration and function that allows markers displayed on other graphs to be moved by moving the cursor of a mouse, which is an input device, on a marker displayed on one of the graphs and then moving the marker on the graph with the mouse. With such a configuration and function, by moving the markers, it is possible to easily grasp the correspondence between the thermal analysis data and the color information data and to evaluate in detail the state changes of the sample accompanying temperature changes.

[0056] Next, referring to FIG. 11 , an example of displaying a thermal analysis data graph and a color information data graph with different variables on the horizontal axis will be described. The DSC data graph displayed at the top of FIG. 11 has temperature on the horizontal axis. DSC data acquired by measuring and then lowering the temperature is typically displayed with temperature on the horizontal axis, with the graph for the temperature rise and the graph for the temperature drop side-by-side. Because the baseline of the DSC data depends on the heat capacity of the sample, the graph for the temperature rise shifts downward and the graph for the temperature drop shifts upward, so the two graphs do not overlap. On the other hand, the RGB color information graphs displayed below the DSC data graph in FIG. 11 without being superimposed on it have time on the horizontal axis. This is because if the RGB graphs were displayed with temperature on the horizontal axis, the graph for the temperature rise and the graph for the temperature drop would overlap, making analysis difficult.

[0057] When a graph of thermal analysis data and a graph of color information data are displayed with different variables on the horizontal axis, it is difficult to grasp the correspondence between the two graphs. Therefore, as shown in FIG. 11 , the marker display means displays markers at corresponding points on each graph (e.g., points at the same measurement time). By displaying markers at corresponding points on each graph, the correspondence between the graph of thermal analysis data and the graph of color information data can be easily grasped. Furthermore, if the marker display means 36 has a configuration and function that allows markers displayed on other graphs to be moved in response to moving a marker displayed on one graph, moving the markers allows detailed evaluation of changes in the state of the sample due to temperature changes while easily grasping the correspondence between the thermal analysis data and the color information data.

[0058] Furthermore, the marker display means 36 may have a configuration and function for moving a marker displayed on a graph in response to the selection of a value within a predetermined temperature or time range using a slider bar. For example, FIG. 11 shows an example in which a slider bar is displayed below a color information data graph, allowing the selection of a value within a predetermined time range. Markers are displayed at points on the thermal analysis graph and color information graph corresponding to the time corresponding to the position of the rectangular knob on the slider bar. The markers move on each graph in response to moving the slider bar knob left or right. This facilitates the easy movement of the markers, making it easier to grasp the correspondence between the thermal analysis data and the color information data and to evaluate in detail the changes in the state of the sample as the temperature changes. Furthermore, to facilitate the adjustment of the slider bar knob position, values ​​on the vertical axis (intensity of color information data) and horizontal axis (time, temperature, etc.) corresponding to the knob position may be displayed near the slider bar.

[0059] Next, the graph display method by the thermal analysis apparatus of the present invention shown in Fig. 14 will be described, while comparing it with the graph display method of the comparative example shown in Fig. 12 and Fig. 13. The DSC data shown in Fig. 12 to Fig. 14 is the same, and was obtained by measuring in a cycle in which the PET was heated to 300°C, cooled to 40°C, and then heated back to 300°C. The color information data shown in Fig. 12 to Fig. 14 is the same, and is color information data (RGB values) generated by selecting a range near the center of the sample image from PET image data taken in synchronization with the above measurements.

[0060] FIG. 12 shows Comparative Example 1, in which a graph of DSC data (DSC, unit: mW), a graph of three color information data (R value, G value, B value), and a graph of sample temperature (unit: °C) are superimposed with time (unit: min) on the horizontal axis. FIG. 13 shows Comparative Example 2, in which a graph of DSC data and a graph of three color information data are superimposed with temperature on the horizontal axis. FIG. 14 shows a graph display method using the thermal analysis instrument of the present invention, in which a graph of DSC data with temperature on the horizontal axis and a graph of three color information data with time on the horizontal axis are displayed one above the other without superimposing. A graph of sample temperature is also displayed on the color information graph.

[0061] As shown in FIG. 14 , according to the present invention, the DSC data graphs are displayed with the horizontal axis representing temperature, with the graphs for the first heating, the first cooling, and the second heating being superimposed. Therefore, it is easy to see that the first graph allows observation of glass transition, crystallization, and melting reactions, while the second graph only allows observation of melting reactions. Although the graphs for the three color information data overlap, the DSC data graph is not superimposed, making analysis difficult. Furthermore, markers are displayed at corresponding points on the DSC data and the three color information data, making it easy to understand the correspondence between the two. Therefore, the thermal analysis data and color information data can be compared and evaluated while easily understanding the correspondence, allowing for detailed evaluation of changes in the state of the sample as the temperature changes. Furthermore, if the position of each displayed marker can be moved by moving the mouse cursor or slider bar, it becomes even easier to compare and evaluate the thermal analysis data and color information data while understanding the correspondence.

[0062] In contrast, in the graph of Comparative Example 1 shown in Fig. 12, the DSC data graph is displayed with time on the horizontal axis, making it difficult to compare and evaluate the graph for the first temperature increase, the graph for the first temperature decrease, and the graph for the second temperature increase. Furthermore, the DSC data graph, the graphs of the three color information, and the graph of the sample temperature are displayed superimposed, making it difficult to analyze each graph in detail and make a comparative evaluation.

[0063] 13, the graphs of the three color information data are difficult to analyze because the graphs for the first temperature rise, the first temperature fall, and the second temperature rise overlap. Also, since it is difficult to grasp the correspondence between the DSC data graph and the color information graph, it is difficult to compare and evaluate these graphs to evaluate in detail the state changes of the sample as the temperature rises.

[0064] Furthermore, the computer 8 on which the software 30 is installed may have the configuration and function of a gradation display means for displaying on the display device 10 a gradation in which colors generated from color information data are arranged corresponding to temperature or time. In FIG. 15, the colors generated by the gradation display means from the R, G, and B values ​​of the color information data shown in FIG. 8 are displayed in the "Color" column. As shown in FIG. 15, the thermal analysis data, image data, color information (R, G, and B values), and generated colors are linked to the measurement time and the sample temperature at that time. Therefore, the generated colors allow the user to visually grasp the color of the sample corresponding to each measurement time and sample temperature.

[0065] Figure 16 shows a gradation (color bar) of colors generated from the color information data (RGB values) displayed in Figure 10 below the graphs of thermal analysis data (DSC data) and color information data (RGB values). The horizontal axis represents time from the start of measurement, and the scale is adjusted accordingly. Because the number of sample images that can be displayed is limited, it is difficult to evaluate color changes in localized areas or to compare and evaluate color changes in multiple areas. A graph of color information data (RGB values) can evaluate areas where the color information changes, but it does not allow for visual assessment of the actual color or color change of the sample. In contrast, a gradation (color bar) of colors generated from the color information data (RGB values) allows for detailed assessment of areas where the color changes occur on the sample, as well as for easy visual assessment of the actual color and color change of the sample. Therefore, by displaying a graph of thermal analysis data and a gradation (color bar) of the sample's color change, it is possible to evaluate in detail the state changes that occur with temperature changes in the sample.

[0066] Example 2 As another embodiment of the thermal analysis apparatus of the present invention, a sample observation type TG-DTA apparatus will be described. Thermogravimetry (TG) is defined as "a method for measuring the mass of a sample as a function of temperature while the sample is changed according to a certain program." Differential thermal analysis (DTA) is "a method for detecting the thermal changes that occur within a sample in association with physical and chemical changes that occur when the sample is heated or cooled, as a temperature difference from a reference sample." The TG-DTA apparatus is a thermal analysis apparatus that can perform both thermogravimetry (TG) and differential thermal analysis (DTA) of a sample. An example of a sample observation type TG-DTA apparatus to which the present invention can be applied is the TG-DTA apparatus described in Japanese Patent No. 6606710.

[0067] A sample observation-type TG-DTA instrument embodying the present invention measures and calculates the physical properties of a sample while changing the sample's temperature by heating or cooling it to obtain thermal analysis data, and also observes and photographs the sample to obtain image data synchronized with the measurement time. A sample observation-type TG-DTA instrument embodying the present invention, or a computer having software installed to control the instrument, includes a thermal analysis graph display means for displaying a graph of the thermal analysis data relative to temperature or time on a display device, a sample image display means for displaying a sample image of the image data on the display device, a color information generation means for generating color information data of a selected range and type from the sample image, a color information graph display means for displaying the graph of the color information data relative to temperature or time side-by-side with the graph of the thermal analysis data relative to temperature or time on the display device, and a marker display means for displaying a marker at any point on one of the graphs and also at points on other graphs whose measurement times are synchronized with the point where the marker was displayed. Furthermore, the marker display means can move markers displayed on other graphs in response to moving a marker displayed on one graph. The marker display means can also move a marker displayed on the graph in response to a value within a predetermined temperature range or time range being selected using a slider bar.

[0068] 17 and 18, a case will be described in which the color information generating means further has a configuration and function that allows selection of multiple ranges for generating color information data from the sample image.

[0069] Thermal analysis data acquired by measuring changes in the state of a sample while changing its temperature using a thermal analysis instrument is data for the entire sample. However, the timing of crystallization and transition of a sample is not uniform throughout the sample and often varies depending on the location within the sample. Therefore, a color information generating means according to another embodiment of the present invention further includes a configuration and function that allows multiple ranges for generating color information data from a sample image captured in synchronization with measurement using a sample observation-type thermal analysis instrument. Referring to FIG. 17 , this color information generating means allows selection of two ranges or locations from the sample image for generating color information. Although not shown in FIG. 17 , the color information generating means can select various types of color information to generate, such as "RGB," "CMYK," "CIE Lab," and "HSV."

[0070] FIG. 18 shows an example of a graph of thermal analysis data and a graph of color information data from multiple locations displayed by a thermal analysis device according to another embodiment of the present invention. The thermal analysis data graphs include a TG data graph with temperature (in °C) on the horizontal axis and mass (in g) on ​​the left vertical axis, and a DTA data graph with temperature (in °C) on the horizontal axis and heat flow (in μV) on the vertical axis. It is also possible to select one or more arbitrary points on the thermal analysis data graph and display sample images for each point. In FIG. 18, sample images for three points on the TD graph are displayed. Sample images can also be displayed on the DTA graph. Furthermore, graphs of color information data (H, S, V) generated from two selected locations on the sample image are displayed below the thermal analysis data graph without overlapping each other.

[0071] As shown in Figure 18, by displaying a graph of thermal analysis data and color information graphs of multiple parts of the sample image that you want to compare side by side without overlapping, you can compare and evaluate changes in the sample's state and the timing of these changes as the sample temperature changes for different parts of the sample.

[0072] When there are many ranges or locations in a sample image for which color information data is to be generated, if the thermal analysis data graph and the color information data graphs for all of the locations are displayed side by side on a display device without being superimposed, the graphs tend to be small and difficult to see. To avoid this, it is possible to select one piece of color information data to display, and display the graphs of the selected color information data for the multiple locations in different colors and superimposed.

[0073] The thermal analysis apparatus and the computer having installed software for controlling the thermal analysis apparatus according to another embodiment of the present invention may further include the configuration and functionality of a gradation display means for displaying on a display device a gradation in which colors generated from color information data are arranged in correspondence with temperature or time. In particular, when there are multiple ranges or locations in a sample image for which color information data is to be generated, the actual color and color changes at each location of the sample can be visually and easily grasped by displaying a gradation (color bar) in which the colors generated from the color information data (RGB values) generated for each of the multiple locations are arranged. Therefore, by analyzing the graphs of the thermal analysis data, the state changes of the sample due to temperature changes can be evaluated in detail for each location of the sample.

[0074] The present invention is not limited to the above-described embodiments, and includes various modifications and equivalents that fall within the scope of the technical idea of ​​the present invention and each component of the present invention.

[0075] For example, the thermal analysis apparatus of the present invention is not limited to one composed of multiple devices, such as a differential scanning calorimetry (DSC) apparatus or a TG-DTA apparatus, a cooling unit, a computer on which control software is installed, an input device, and a display device, but may also be one in which some or all of these devices are integrated. Furthermore, a computer on which control software is installed may control multiple differential scanning calorimetry (DSC) apparatuses or TG-DTA apparatuses or other thermal analysis apparatuses. Furthermore, some or all of the control software may be installed on a cloud server.

[0076] The thermal analysis device of the present invention is not limited to a differential scanning calorimetry (DSC) device or a TG-DTA device, but may be a thermogravimetry (TG) device, a differential thermal analysis (DTA) device, a thermomechanical analysis (TMA) device, or any other type of thermal analysis device. [Industrial Applicability]

[0077] The present invention can be used to provide a thermal analysis device that can analyze changes in the state of a sample in detail while closely understanding and correlating changes in the color of the sample that accompany changes in the temperature of the sample, and control software for realizing such a thermal analysis device. [Explanation of symbols]

[0078] 1: Thermal analyzer, 2: Differential scanning calorimetry (DSC) device, 3: Automatic sample changer, 4: Cooling unit, 5: Lid with observation window, 6: Camera, 7: Camera movement mechanism, 8: Computer, 9: Input device, 10:Display device, 11: Case, 12, 13: Heat insulation material, 14:Heating furnace, 14a: heater, 15:Measurement room, 16: Thermal plate, 17, 18: sample container, 19: Sample temperature detection means, 20: Reference material temperature detection means; 21: heating furnace temperature detection means, 22: refrigerant jacket, 23: Case lid, 24: Inner lid with observation window, 25: Inner lid with observation window, 26: Outer cover with observation window, 27: Central Processing Unit (CPU), 28: Graphics Processing Unit (GPU), 29: Storage device, 30: Control software, 31: Thermal analysis graph display means, 32: Sample image display means, 33: Color information generation means, 34: Color information graph display means, 35: Marker display means

Claims

1. A thermal analysis apparatus that measures and calculates the physical properties of a sample while changing the temperature of the sample by heating or cooling the sample to obtain thermal analysis data, and also photographs the sample to obtain image data, a thermal analysis graph display means for displaying a graph of the thermal analysis data relating to temperature or time on a display device; a sample image display means for displaying a sample image of the image data on the display device; a color information generating means for generating color information data of a selected range and type from the sample image; a color information graph display means for displaying a graph of the color information data relating to temperature or time on the display device, side by side with the graph of the thermal analysis data relating to temperature or time without superimposing the graph; a marker display means for displaying a marker at an arbitrary point on one of the graphs, and also displaying markers at other points on the graphs whose measurement times are synchronized with the point at which the marker is displayed; The thermal analysis apparatus is characterized in that the thermal analysis graph display means and the color information graph display means display one of the thermal analysis data and the color information data as a graph related to temperature and the other as a graph related to time, and the marker display means displays each of the markers individually and identifiably at points on each of the graphs where measurement times are synchronized.

2. A thermal analysis device that measures and calculates the physical properties of a sample while changing the temperature of the sample by heating or cooling, thereby obtaining thermal analysis data, and also photographs the sample to obtain image data, a thermal analysis graph display means for displaying a graph of the thermal analysis data relating to temperature or time on a display device; a sample image display means for displaying a sample image of the image data on the display device; a color information generating means for generating color information data of a selected range and type from the sample image; a color information graph display means for displaying a graph of the color information data relating to temperature or time on the display device, side by side with the graph of the thermal analysis data relating to temperature or time without superimposing the graph; a marker display means for displaying a marker at an arbitrary point on one of the graphs, and also displaying markers at other points on the graphs whose measurement times are synchronized with the point at which the marker is displayed; The thermal analysis apparatus is characterized in that the thermal analysis graph display means displays a graph relating to the temperature of the thermal analysis data in which a plurality of thermal analysis data values ​​correspond to the same temperature as the temperature of the sample increases and decreases, and the marker display means displays each of the markers individually and identifiably at points on the thermal analysis data graph and the color information data graph where the measurement times are synchronized.

3. 3. The thermal analysis apparatus according to claim 1, wherein the marker display means moves markers displayed on other graphs in response to movement of a marker displayed on one graph.

4. 3. The thermal analysis apparatus according to claim 1, wherein the marker display means moves a marker displayed on the graph in response to a value within a predetermined temperature range or time range being selected using a slider bar.

5. 3. The thermal analysis apparatus according to claim 1, wherein the color information generating means can select a plurality of ranges for generating color information data from the sample image.

6. a computer that controls a thermal analysis device that measures and calculates the physical properties of a sample while changing the temperature of the sample by heating or cooling the sample to obtain thermal analysis data, and also photographs the sample to obtain image data; a thermal analysis graph display means for displaying a graph of the thermal analysis data relating to temperature or time on a display device; a sample image display means for displaying a sample image of the image data on the display device; color information generating means for generating color information data of a selected range and type from the sample image; a color information graph display means for displaying a graph of the color information data relating to temperature or time on the display device, side by side with the graph of the thermal analysis data relating to temperature or time without superimposing it on the graph; and A thermal analysis apparatus control software that functions as a marker display means that displays a marker at an arbitrary point on one of the graphs and also displays markers at other points on the graphs whose measurement times are synchronized with the point at which the marker is displayed, The thermal analysis graph display means and the color information graph display means display one of the thermal analysis data and the color information data as a graph related to temperature and the other as a graph related to time, and the marker display means displays each of the markers individually and identifiably at points on each of the graphs where measurement times are synchronized.

7. A computer that controls a thermal analysis device that measures and calculates the physical properties of a sample while changing the temperature of the sample by heating or cooling it to obtain thermal analysis data, and also photographs the sample to obtain image data, a thermal analysis graph display means for displaying a graph of the thermal analysis data relating to temperature or time on a display device; a sample image display means for displaying a sample image of the image data on the display device; color information generating means for generating color information data of a selected range and type from the sample image; a color information graph display means for displaying a graph of the color information data relating to temperature or time on the display device, side by side with the graph of the thermal analysis data relating to temperature or time without superimposing it on the graph; and A thermal analysis apparatus control software that functions as a marker display means that displays a marker at an arbitrary point on one of the graphs and also displays markers at other points on the graphs whose measurement times are synchronized with the point at which the marker is displayed, The thermal analysis graph display means displays a graph relating to the temperature of the thermal analysis data in which a plurality of thermal analysis data values ​​correspond to the same temperature as the temperature of the sample increases and decreases, and the marker display means displays each of the markers individually and identifiably at points on the thermal analysis data graph and the color information data graph where the measurement times are synchronized.

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