Method for evaluating a measurement result of a thermal analysis, as well as use of the method, computer unit, computer program product and system for performing the method
09816869 · 2017-11-14
Assignee
Inventors
- Thomas Denner (Selb, DE)
- Juergen Blumm (Selb, DE)
- Otto Max Schaefer (Selb, DE)
- Markus Hollering (Wunsiedel, DE)
- Thilo Hilpert (Selb, DE)
- Alexander Frenzl (Schoenwald, DE)
- Stefan Lauterbach (Selb, DE)
- Andreas Strobel (Auerbach, DE)
- Gabriele Kaiser (Selb, DE)
- Stephan Knappe (Doehlau, DE)
- Rolf Preuss (Einbeck, DE)
- Michael Gebhardt (Selb, DE)
- Elena Moukhina (Selb, DE)
- Alexander Schindler (Leupoldsgruen, DE)
- Matthias Gradl (Sesslach, DE)
- Gunther Herr (Haarth, DE)
- André Nijmeh (Merkendorf, DE)
- Stefan Schmoelzer (Issigau, DE)
- Markus Meyer (Ehingen, DE)
Cpc classification
G06F17/16
PHYSICS
G01N25/20
PHYSICS
G06F17/18
PHYSICS
International classification
G01K1/00
PHYSICS
G01K5/00
PHYSICS
G01K3/10
PHYSICS
G01K9/00
PHYSICS
G01K11/00
PHYSICS
G01K7/00
PHYSICS
G06F17/16
PHYSICS
G01N25/20
PHYSICS
G06F17/18
PHYSICS
Abstract
A method for evaluating a measurement result of a thermal analysis. A program-controlled computer unit is used to calculate at least one probability of the agreement of the measurement result with at least one dataset previously stored in the computer unit, wherein this calculation is based on a comparison of effect data previously extracted from a measurement curve of the thermal analysis with corresponding stored effect data of the dataset. The evaluation can advantageously include, an automatic recognition and classification of measurement curves and can be carried out in particular more efficiently, more economically and more quickly than previously, with at the same time a high quality of evaluation.
Claims
1. A method for evaluating a measurement result of a thermal analysis, comprising the step of: calculating, via a program controlled computer unit, a plurality of probabilities of an agreement of the measurement result with a plurality of datasets previously stored in the computer unit in order to identify at least one probability of the plurality of probabilities, wherein the calculation is based on a comparison of effect data previously extracted from a measurement curve of the thermal analysis with corresponding stored effect data of the dataset.
2. The method according to claim 1, wherein the effect data comprises at least minima, maxima and steps in the course of the measurement curve.
3. The method according to claim 1, wherein the effect data for each effect are represented as a given feature vector, the feature vector having vector components which represent quantitatively specific properties of the effect concerned.
4. The method according to claim 1, further comprising the step of extracting the effect data from the measurement curve of the thermal analysis using the computer unit.
5. The method according to claim 4, further comprising the step of processing the measurement curve using the computer unit before extracting the effect data from the measurement curve.
6. The method according to claim 1, further comprising the step of assigning the measurement result to the at least one dataset using the computer unit, wherein the assignment is based on a result of the calculation of one or more agreement probabilities.
7. Use of a method for evaluating a measurement result of a thermal analysis, the use of the method in an area of quality assurance in production or processing of goods, comprising the steps of: performing a thermal analysis on produced or processed goods at least on a random sample basis, evaluating the measurement result of the thermal analysis by means of a method that includes calculating, via a program controlled computer unit, at least one probability of an agreement of the measurement result with at least one dataset previously stored in the computer unit, wherein the calculation is based on a comparison of effect data previously extracted from a measurement curve of the thermal analysis with corresponding stored effect data of the dataset, wherein an assignment of a given measurement result takes place to one of a plurality of quality classes and/or an interpretation of the given measurement result takes place.
8. A computer unit integrated into or connected to a device for performing a thermal analysis, the computer unit having instructions executing on computer readable medium for: calculating, via a program controlled computer unit, at least one probability of an agreement of the measurement result with at least one dataset previously stored in the computer unit, wherein the calculation is based on a comparison of effect data previously extracted from a measurement curve of the thermal analysis with corresponding stored effect data of the dataset.
9. A computer program product containing instructions for automated performance of a thermal analysis by means of a processing system, the computer program product executing on the processing system for: calculating, via a program controlled computer unit, at least one probability of an agreement of the measurement result with at least one dataset previously stored in the computer unit, wherein the calculation is based on a comparison of effect data previously extracted from a measurement curve of the thermal analysis with corresponding stored effect data of the dataset.
10. A system, comprising: a device performing a thermal analysis, and a computer unit configured to evaluate a measurement result of the thermal analysis by calculating at least one probability of an agreement of the measurement result with at least one dataset previously stored in the computer unit, wherein the calculation is based on a comparison of effect data previously extracted from a measurement curve of the thermal analysis with corresponding stored effect data of the dataset.
11. The method according to claim 2, wherein the effect data further comprises maxima, minima and steps in the course of a derivative of the course of the measurement curve.
12. The method according to claim 1, wherein the plurality of probabilities comprises a probability for each of the plurality of datasets, each probability representing similarities or differences.
13. The method according to claim 1, wherein the plurality of datasets comprises more than twenty datasets.
14. The method according to claim 1, wherein the at least one probability identifies a material class for a substance.
15. The method according to claim 1, wherein the at least one probability identifies a quality class for a substance.
16. The method according to claim 5, wherein the step of processing comprises at least one of the following: smoothing; filtering; eliminating a region; subtracting an empty curve.
17. The method according to claim 1, wherein extraction of effect data from the measurement curve comprises segmentation of the measurement curve, where the measurement curve is split up into regions for further evaluation.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The invention will be described further below with the aid of examples of embodiment making reference to the appended drawings. In the figures:
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
DETAILED DESCRIPTION OF THE INVENTION
(12)
(13) The method represented in
(14)
(15) As can be seen from
(16) With regard to
(17) The preliminary processing can comprise in particular the subtraction of the so-called empty curve of the measuring device, but alternatively or in addition also for example smoothing, averaging or filtering of the measurement curve, the omission of unimportant regions or a mathematical standardisation of the measurement curve to uniform measurement conditions (e.g. in respect of sample mass and/or heating rate).
(18) Apart from the “untreated” (directly obtained) DSCsample′ measurement curve (continuous line), the empty curve of the analysis device concerned is also plotted with a dashed line in
(19)
(20) With regard to
(21) Segmentation means the splitting-up of the measurement curve into meaningful regions for the subsequent processing. This means that characteristic signal changes attributable to physical effects in the course of the DSCsample measurement curve are detected or identified at least with regard to their temperature-related position and their “type”.
(22) Quite generally, local maxima, minima or steps in the signal concerned, here of the DSC(T) signal, can in particular occur, for example, as characteristic effects in the measurement curve. These effects appearing in the DSCsample measurement curve are based on phase transitions or other endothermic or exothermic processes in the investigated sample. These effects in the DSCsample measurement curve are identified and demarcated from one another by means of a suitable segmentation algorithm running on the computer unit. This can take place in a straightforward manner, for example by taking account of threshold values of the changes in the measurement signal and the changes in the derivative DSCsample(T)/dT of the DSCsample(T) measurement signal.
(23)
(24) In the example described here (
(25) In the example represented, the maximum and the minimum of the DDSC(T) derivative arise approximately at T=245° C. (maximum) and respectively T=256° C. (minimum).
(26) The temperature range of the entire effect, here of the effect type “maximum”, i.e. originating from an endothermic effect in the sample (e.g. due to melting) is highlighted in
(27) As a start of the effect, a temperature could for example be established at which the amount (absolute value) of the DDSC(T) derivative exceeds a threshold value predetermined by means of the algorithm employed.
(28) A mean temperature (“peak”) of the effect can then be determined (or preferably in step S3 described below) by means of the employed algorithm on the basis of the maximum of the DSC(T) measurement signal.
(29) An end of the effect can finally be established for example at the temperature at which the amount of the DDSC(T) derivative falls below a threshold value predetermined by means of the algorithm employed.
(30) In the example described here (
(31) The temperature range of this effect can again be defined by means of a threshold value for the DDSC(T) derivative.
(32) The significance or detection sensitivity for the aforementioned effect types can be defined for example by the fact that the absolute values of the maxima in the DSC(T) signal and the DDSC(T) derivative must exceed specific threshold values. For example, the maximum in the DDSC(T) derivative approximately at T=169° C., which can also be seen in the DSCsample measurement curve from
(33) With regard to
(34) In step S3, the determination of a further start temperature and a further end temperature can in particular be carried out, for example, for each of the effects or at least the effects of at least one specific effect type. This determination can be carried out for example according to known standards such as for example DIN 51007 or ASTM E 53765, in order to determine a (further) start temperature usually referred to as “onset” and/or a (further) end temperature usually referred to as “end”. These temperature values can then enter as corresponding vector components into the respective feature vector. Their calculation can be based in particular on the use of a tangent method (see for example the methods provided for this in the aforementioned standards).
(35) Furthermore, the aforementioned evaluations in respect of a mean temperature (“peak”) and/or (at least for maxima and minima) of one or more curve integrals can be provided in step S3. For the calculation of a curve integral (e.g. area beneath a maximum or minimum), one of the mentioned start temperatures and one of the mentioned end temperatures can for example be used as range limits for the integration.
(36) Steps S2 and S3 can take place semi-automatically, i.e. software-supported, or fully automatically, i.e. completely by means of software. The effect features, which generally relate to the position, the size and the form of the previously identified effects, are placed for each existing effect in each case in a feature vector.
(37)
(38) In the example according to
(39) The features for the glass transition approximately at T=85° C. are here the extrapolated variables “onset” (start temperature), “mid” (midpoint temperature), “end” (end temperature), “delta Cp” (step height).
(40) The properties “onset” and “end”, as well as the properties “peak” (temperature of the maximum) and “area” (area) were also evaluated for the “endothermic peak” (maximum) approximately at T=250° C.
(41) The numerical values indicated in
(42) With regard to
(43)
(44) Measurement curve DSCref1 shown by a dashed line in
(45) The above list “DSCref1, DSCref2, DSCref3, . . . ” is intended to express the fact that a large number of such curves can be previously stored in the computer unit, for example more than 20 or more than 100. In this regard, it should again be noted that the number of such previously stored known curves, or more precisely the effect data corresponding to such curves, can be provided in a variable manner also for operational purposes.
(46) Step S4 delivers as a result a measure of the similarity or agreement probability of effects and ultimately of the measurement curves in question (here, unknown measurement curve DSCsample vs. measurement curve DSCref1 from the database of the computer unit). The variables similarity and agreement probability between measurement curves are complementary to the difference between the measurement curves.
(47) For the purpose of calculation, the (calculated) feature vectors generated in step S3 are used as input variables for a comparison algorithm of the evaluation software. The comparison algorithm can work for example according to a numerical or analytical algorithm, or also according to a statistical algorithm. An agreement probability p can for example be expressed as follows:
p=fp(position)×fg(size)×ff(form),
(48) wherein fp, fg and ff represent agreement probabilities in respect of position, size and form of the effects, and wherein the corresponding effect features determined in step S4 from the measurement curve DSCample and the effect data stored for the reference curve DSCref1 are used for the calculation of fp, fg and ff.
(49) Similar curves can thus be found through high agreement probability, as illustrated in
(50) Through such comparisons of measurement curve DSCsample with each of the previously stored reference measurement curves DSCref1, DSCref2, DSCref3, . . . , the unknown curve DSCsample or the underlying sample can thus be identified and/or characterised and/or classified.
(51) With regard to the possibility of a “classification” of the underlying sample, i.e. an assignment of the measurement result concerned to one of one or more previously defined classes (e.g. quality classes, material classes, etc.), reference is made to the explanations already provided above (and to the following explanation with reference to
(52) If, for example, it is known that the similar measurement curve DSCref1 from the database is a measurement on a specific polymer “X”, the unknown measurement curve DSCsample will have also been measured with a high probability on polymer X. With a high degree of probability, the unknown sample substance is therefore polymer X.
(53) Finally, in the example represented, a step S5 is also provided, in which a further interpretation of the result from step S4 is carried out.
(54) Here, further interpretations can be derived from the effects ascertained after performing steps S1 to S4, their features and the calculated agreement probabilities (similarities or differences). Qualitative and also quantitative differences from the stored curves compared to curves DSCref1, DSCref2, DSCref3, . . . , which can also be used to calculate new variables, can be used as decision criteria for evaluating an unknown measurement curve, such as for example the represented DSCsample curve.
(55) If the described evaluation method is used for example as a measurement method in the area of quality assurance in the production of goods, decisions regarding the process of the quality assurance or the production of the goods can in turn be derived from the results of step S4, and as the case may be step S5 (see also in this regard the explanation given below).
(56) In the example according to
(57) Furthermore, within the scope of the invention, new measurement curves can be added to the databases of the known measurement curves. No knowledge about the measurement curve, but only a designator or name for the measurement curve is required for this purpose.
(58) In an embodiment, the evaluation method described above is carried out at least with steps S1 to S4 in a system which comprises both a device for performing a thermal analysis and a computer unit which is designed for the evaluation of a measurement result of the thermal analysis. The same or another program-controlled computer unit can be used to control the operation of the device for performing the thermal analysis.
(59) Various variants of a comparison between an unknown measurement result with a plurality of known measurement results stored in a database are again explained below by reference to
(60) The effect-based and feature-based evaluation method according to the invention (see for example the example of embodiment according to
(61) In
(62)
(63) These unknown DATAsample effect data are then compared with effect data DATAref1, DATAref2, DATAref3, . . . previously stored in the computer unit as datasets. The arrows and question marks (“?”) entered by way of example in
(64) As symbolised in
(65) Accordingly, features alone (i.e. without an actual measurement curve) can also be stored in the database as unknown “virtual measurement curves” and can be used as reference input variables of the method. This in turn means that the method can also be used as a database search method without an unknown measurement in the original sense. This is illustrated by
(66)
(67) As already mentioned, the evaluation method can also comprise the step of an assignment of a measurement result (DATAsample effect data) to one of a plurality of previously defined classes of datasets (DATAref1, DATAref2, DATAref3, . . . ). Such an assignment can be carried out on the basis of the result of the calculation of the agreement probabilities. This development is illustrated by
(68)
(69)
(70) In this method, the mentioned classes (here for example classes C1 and C2) of the stored measurement curves are groups of measurement curves belonging to a class (e.g. “substance class” of the sample). The user himself can group existing measurement curves (such as DATAref1, DATAref2, DATAref3, . . . ) by suitable user inputs and obtains by the method, for a new measurement curve (such as DSCsample or DATAsample), the given probabilities of belonging to various existing classes.
(71) As a result of the grouping by the user, the method can be increasingly trained in respect of the classification with suitable configuration of the software, without the basic mathematical parameters having to be modified. This has the advantage that the calculation of the agreement probability between different measurement curves can remain independent of the grouping of the measurement curves by the user and the algorithm of the method is therefore robust.
(72)
(73) System 10 comprises a device 12 for performing a thermal analysis, which can be constituted in a manner known per se, i.e. for example comprising a regulatable temperature-controlled furnace for the temperature control of a sample and a sensor for detecting operational parameters (e.g. furnace temperature) and the measurement signal or signals to be recorded (e.g. DSC signal, sample mass signal, sample length signal etc.).
(74) Furthermore, in the example represented, system 10 comprises a computer unit 14, which controls in a manner known per se the operation (e.g. course of a specific temperature-control program) of thermal analysis device 12 and records the desired measurement signal or signals (in particular, for example, a DCS signal).
(75) For this purpose, computer unit 14 is connected to thermal analysis device 12 via a control interface 16 and a sensor interface 18. In particular, the control of a furnace heating device contained in device 12 can for example take place via (e.g. digital) control interface 16, whereas the measurement signal or signals obtained by means of the sensor device(s) concerned (see for example DCSsample′ in
(76) Moreover, an evaluation method of the already described kind is also implemented by means of a computer unit 14 or the software running thereon, so that an evaluation of a measurement result of the thermal analysis obtained by means of thermal analysis device 12 can advantageously be carried out at the same time by means of system 10.
(77) System 10 is also suitable, for example, particularly as a measuring system which is used in quality assurance (including “process control”) in a production process (including “processing process” in the narrower sense).
(78) Effects, whose features or similarities between effects or whole measurement curves, such as can be obtained by the rapidly performable evaluation, can serve as quality criteria. Samples investigated by means of system 10 can thus be split up, for example, into various quality classes, e.g. into classes “good parts” and “bad parts”.
(79) This can take place, for example, by means of the classification method described by reference to
(80) For example, additionally detected effects in the measurement curve (compared to known effect data) can indicate impurities of the sample. Additional effects can, moreover, provide information about the previous thermal history or previous thermal treatment of a material, i.e. how the input material in storage or production has been heat-treated. As already mentioned above, a degree of crystallinity or the potential for post-crystallisation (or also for post-crosslinking or post-curing), for example, can also be calculated from the magnitude of an effect (of the “crystallisation peak” or the “crosslinking peak”), which correlates with the mechanical values (hardness, rigidity) of the sample, this often being an important property of the finished part.
(81) On account of the speed of the evaluation method, a further interpretation of the curve recognition (see for example step S5 in the example of embodiment described above) can advantageously be applied in-situ or online in the process.
(82) To save time, it is also possible for example for an ongoing measurement to be terminated prematurely on account of a specific result of the further interpretation of the curve recognition.
(83) The already mentioned “bad parts” of a production process can for example be removed online (controlled by the computer unit concerned).
(84) An entire production process, i.e. machines employed for this, could be stopped or the settings on the machines could be changed online-based on the results of the evaluation, in particular for example the further interpretation of the effect data comparison result.
(85) For example, a tool temperature to be adjusted can be an important influencing parameter on the aforementioned degree of crystallinity of the samples or of the finished parts. That is to say that the tool temperature can be adapted before, during and/or after the performance of the process. Furthermore, a machine for opening and removing a finished part, for example, could be triggered on the basis of the evaluation result. Cycle times in the process can thus be reduced and productivity increased. Finally, raw materials required for production could also be metered in their quantity, i.e. their quantity ratios could be adapted, by using the invention.
(86)
(87) System 10a according to
(88) The modification of system 10a consists in the fact that, instead of a computer unit used in common for the thermal analysis control and the analysis evaluation, it comprises two separately implemented computer units 14a-1 and 14a-2.
(89) First computer unit 14a-1 serves in a manner known per se to control the operation (e.g. course of a specific temperature control program) of thermal analysis device 12a and to record the desired measurement signal or signals. Computer unit 14a-1 is structurally combined with device 12a (here: accommodated together with device 12a in a common device housing).
(90) In contrast with this, second computer unit 14a-2 constituted separately therefrom, but being in a communication connection with first computer device 14a-1, serves to carry out the evaluation method of the described type, so that an evaluation of a measurement result obtained by means of thermal analysis device 12a can at the same time be advantageously carried out by means of system 10a.
(91) In the example represented according to
(92)
(93) In the case of the system use or quality assurance according to
(94) For this purpose, plant 20b comprises two processing stations (machines) 22b-1 and 22b-2 in the represented example. These stations 22b-1, 22b-2, passed through successively, thus form a production and processing path for the production of end products 26b.
(95) In the example represented, products are removed from their conveyance along the production and processing path at least on a random sample basis at three points (see dashed arrow at E1, E2 and E3) for the performance of the quality assurance, are subjected to the thermal analysis by means of thermal analysis device 12b and are transferred back into the processing path at the same point in each case (A1, A2 and A3 respectively).
(96) As already described for the preceding example from
(97) Depending on the results of these analyses, an intervention into the production and processing process takes place as required and automatically (initiated by computer unit 14b-2). For this purpose, the communication or operative connections represented in
(98) To sum up, the invention provides in particular an advantageous method for the automatic recognition and classification of measurement curves in the area of thermal analysis as well as the application of such a method in processes, e.g. industrial processes of quality assurance or production.