Crystallinity measuring device, crystallinity measuring method, and information storage medium

Abstract

This invention provides a crystallinity measuring device, comprising: a measurement pattern acquisition unit for acquiring an X-ray scattering pattern of a sample containing a target substance and other known mixed substances; a known pattern acquisition unit for acquiring a known X-ray scattering pattern of the mixed substances; a crystallization pattern acquisition unit for acquiring, based on the X-ray scattering pattern of the sample, at least partially acquiring an X-ray diffraction pattern of the crystalline portion of the target substance; a crystallization integral intensity calculation unit for calculating the integral intensity related to the X-ray diffraction pattern of the acquired crystalline portion; a target substance integral intensity calculation unit for calculating the integral intensity related to the X-ray scattering pattern of the target substance based on the X-ray scattering pattern of the sample and the known X-ray scattering pattern; and a crystallinity calculation unit for calculating the crystallinity of the target substance based on the integral intensity related to the X-ray diffraction pattern of the crystalline portion and the integral intensity related to the X-ray scattering pattern of the target substance.

Description

Technical Field

[0001] This invention relates to a crystallinity measuring device, a crystallinity measuring method, and an information storage medium, and particularly to the measurement of crystallinity using X-ray diffraction. Background Technology

[0002] Polymers include crystalline polymers and amorphous polymers, but even crystalline polymers are not entirely crystalline; crystalline and amorphous portions are mixed together. The ratio of the weight of the crystalline portion to the total weight of the crystalline polymer is called its crystallinity. Crystallinity is important information for understanding the mechanical and chemical properties of crystalline polymers.

[0003] Among various methods for measuring crystallinity, the X-ray diffraction method has significant practical advantages, such as being independent of sample size and being able to perform sample analysis non-destructively. Summary of the Invention

[0004] The technical problem to be solved by the present invention

[0005] In X-ray diffraction, the crystallinity of a material is the value of the integral intensity of the scattering pattern (in this case, the diffraction pattern) from the crystalline portion of the material divided by the sum of the integral intensities of the scattering patterns from the crystalline and amorphous portions (i.e., the integral intensity of the scattering pattern of the entire material).

[0006] Therefore, to determine crystallinity, it is necessary to accurately identify at least the scattering pattern (diffraction pattern) from the crystalline portion. However, the diffraction pattern from the crystalline portion is difficult to determine because the diffraction intensity is weak in the high-angle region and is buried in the scattering patterns from the amorphous portion and other substances. Furthermore, when the crystalline polymer is mixed with other mixed substances such as fillers, especially with amorphous mixed substances such as glass fibers, it is difficult to separate the scattering pattern from the mixed substances.

[0007] The present invention was made in view of the above-mentioned problems, and its object is to provide a crystallinity measuring device, a crystallinity measuring method, and an information storage medium that can more accurately measure the crystallinity of a substance using X-ray diffraction.

[0008] Technical solutions for solving technical problems

[0009] To address the aforementioned problems, the crystallinity measuring device of the present invention comprises: a measurement pattern acquisition unit, which acquires the X-ray scattering pattern of a sample containing a target substance and other known mixed substances; a known pattern acquisition unit, which acquires a known X-ray scattering pattern of the mixed substances; a crystallization pattern acquisition unit, which, based on the X-ray scattering pattern of the sample, at least partially acquires the X-ray diffraction pattern of the crystalline portion contained in the target substance; a crystallization integral intensity calculation unit, which calculates the integral intensity related to the X-ray diffraction pattern of the acquired crystalline portion; a target substance integral intensity calculation unit, which, based on the X-ray scattering pattern of the sample and the known X-ray scattering pattern, calculates the integral intensity related to the X-ray scattering pattern of the target substance; and a crystallinity calculation unit, which calculates the crystallinity of the target substance based on the integral intensity related to the X-ray diffraction pattern of the crystalline portion and the integral intensity related to the X-ray scattering pattern of the target substance.

[0010] Furthermore, the crystallinity measurement method of the present invention includes: a measurement pattern acquisition step, which acquires an X-ray scattering pattern of a sample containing a target substance and other known mixed substances; a known pattern acquisition step, which acquires a known X-ray scattering pattern of the mixed substances; a crystallization pattern acquisition step, which, based on the X-ray scattering pattern of the sample, at least partially acquires an X-ray diffraction pattern of the crystalline portion contained in the target substance; a crystallization integral intensity calculation step, which calculates the integral intensity related to the X-ray diffraction pattern of the acquired crystalline portion; a target substance integral intensity calculation step, which, based on the X-ray scattering pattern of the sample and the known X-ray scattering pattern, calculates the integral intensity related to the X-ray scattering pattern of the target substance; and a crystallinity calculation step, which calculates the crystallinity of the target substance based on the integral intensity related to the X-ray diffraction pattern of the crystalline portion and the integral intensity related to the X-ray scattering pattern of the target substance.

[0011] Furthermore, the information storage medium involved in this invention is a computer-readable information storage medium, which stores a program for causing a computer to perform the following steps: a measurement pattern acquisition step, which acquires an X-ray scattering pattern of a sample containing the object substance being measured and other known mixed substances; a known pattern acquisition step, which acquires a known X-ray scattering pattern of the known mixed substances; a crystallization pattern acquisition step, which, based on the X-ray scattering pattern of the sample, at least partially acquires an X-ray diffraction pattern of the crystalline portion of the object substance; a crystallization integral intensity calculation step, which calculates the integral intensity related to the X-ray diffraction pattern of the acquired crystalline portion; an object substance integral intensity calculation step, which calculates the integral intensity related to the X-ray scattering pattern of the object substance based on the X-ray scattering pattern of the sample and the known X-ray scattering pattern; and a crystallinity calculation step, which calculates the crystallinity of the object substance based on the integral intensity related to the X-ray diffraction pattern of the crystalline portion and the integral intensity related to the X-ray scattering pattern of the object substance. Attached Figure Description

[0012] Figure 1 This is a structural diagram of the crystallinity measuring device according to an embodiment of the present invention.

[0013] Figure 2 A diagram illustrating an example of an X-ray scattering pattern of a sample.

[0014] Figure 3 A diagram illustrating an example of an X-ray scattering pattern of a mixed substance.

[0015] Figure 4 A diagram illustrating an example of an X-ray scattering pattern of an object.

[0016] Figure 5 A diagram schematically representing the X-ray diffraction pattern of the crystalline portion of a material.

[0017] Figure 6 A diagram illustrating an example of the initial X-ray scattering pattern of a sample.

[0018] Figure 7 A graph showing the relationship between the integral range and the integral value of the intensity.

[0019] Figure 8 This is a flowchart illustrating the process of calculating the scaling factor.

[0020] Figure 9 This is a flowchart illustrating the crystallinity calculation process involved in the first embodiment.

[0021] Figure 10This is a flowchart illustrating the crystallinity calculation process involved in the second embodiment. Detailed Implementation

[0022] The following describes one embodiment of the present invention in detail with reference to the accompanying drawings.

[0023] (Device Composition)

[0024] Figure 1 This is a configuration diagram of a crystallinity measuring apparatus according to one embodiment of the present invention. As shown, the crystallinity measuring apparatus 10 includes an X-ray diffraction device 12, a calculation unit 14, a storage unit 16, and a display unit 18. Furthermore, when calculating crystallinity based on a measurement pattern obtained from another X-ray diffraction device, the crystallinity measuring apparatus 10 need not include the X-ray diffraction device 12. In this case, the crystallinity measuring apparatus 10 can be composed of the calculation unit 14, the storage unit 16, and the display unit 18, with the measurement pattern obtained from another X-ray diffraction device pre-stored in the storage unit 16.

[0025] X-ray diffraction apparatus 12 performs X-ray diffraction measurements. Specifically, X-ray diffraction apparatus 12 incident X-rays of known wavelength onto a sample and measures the intensity of the scattered rays. Data on the X-ray intensity at each diffraction angle 2θ is output from X-ray diffraction apparatus 12 as a measurement pattern to processing unit 14. Furthermore, the measurement pattern output to processing unit 14 can be corrected using the Lorentz polarization factor (Lp correction). X-ray emission apparatus 12 is capable of measuring sufficiently small minimum angles 2θ from approximately 10 degrees. L To a sufficiently large 2θ of approximately 120 degrees H The intensity of scattered X-rays at each diffraction angle of the maximum angle. Furthermore, in this specification, the curve of X-ray intensity measured by the X-ray diffraction apparatus 12 (showing data on how X-ray intensity changes with the diffraction angle) is referred to as the "X-ray scattering pattern". In the case of a crystalline sample, the X-ray scattering pattern is particularly referred to as the "X-ray diffraction pattern".

[0026] In this embodiment, the sample being processed is a known substance (the mixed substance) that is a powder or a flowable polymer, partly crystalline and partly amorphous, mixed with one or more fillers or other powders. When preparing the sample, the types and weight ratios of the various substances constituting the sample are known. The chemical formula and chemical amount of each substance are also known. Furthermore, the X-ray scattering pattern of the mixed substance is also known. In the following description, the measured substance is considered as a bulk solid. When synthesizing such a measured substance, a powdered or fluid polymer and various fillers or other known substances are mixed. These mixtures are then molded and heat-treated to produce a resin material that serves as the sample. Furthermore, this invention is applicable not only to bulk solid samples but also to powdered samples.

[0027] The arithmetic unit 14 is configured as, for example, a known computer system, including a CPU and memory. The arithmetic unit 14 is connected to a storage unit 16, which is configured as a computer-readable information storage medium such as an SSD (Solid State Disk) or HDD (Hard Drive Disk). The storage unit 16 stores a crystallinity measurement program according to an embodiment of the present invention, and this program is executed by the arithmetic unit 14 to realize the apparatus and method according to an embodiment of the present invention. Furthermore, the storage unit 16 also stores chemical formula information (chemical formula, formula weight, number of electrons per atom in the relevant substance) and weight ratio of each substance contained in the sample. Additionally, it also stores X-ray scattering patterns of the mixed substances.

[0028] Display unit 18 is a display device that displays the calculation results of calculation unit 14. For example, display unit 18 displays the crystallinity of the target substance through numerical values ​​and graphs.

[0029] (Overview of sample measurement and crystallinity calculation)

[0030] Figure 2 To schematically represent the y-axis of the X-ray scattering pattern of the sample being measured. BP_obs An example of this is shown in the figure. The figure illustrates the X-ray scattering pattern y. BP_obs The X-ray scattering pattern of the sample is measured by the X-ray diffraction apparatus 12 and stored in the storage unit 16. Furthermore, as will be described later, the X-ray scattering pattern of the sample is from a minimum value of 2θ. L to the cutoff angle 2θ T The measured (2θ) within the limited angular range T <2θ H ).

[0031] As mentioned above, a sample can contain multiple mixed substances; here, we assume it contains one mixed substance. Figure 3 The image shows the X-ray scattering pattern of this mixed material. x BP-obs One example. The pattern shown in the figure can be a pattern pre-measured by X-ray diffraction device 12, or a pattern measured by other X-ray radiation devices. X-ray scattering pattern y of the mixed material. x BP-obs It is at 2θ L up to 2θ H The X-ray scattering pattern of the mixed material was created within the angular range. x BP-obs Pre-stored in storage unit 16. The X-ray scattering pattern y of the mixed material. x BP-obs The background intensity, represented by the dashed line in the figure, is also stored in the storage unit 16. If the X-ray diffraction pattern of the crystallized substance of each individual component in the mixture or a crystalline substance with a composition similar to that of the mixture is measured in advance, the background intensity can be easily extracted from it.

[0032] Furthermore, the mixed substances can be amorphous, crystalline, or a mixture of both. In the case of crystallization, the X-ray scattering pattern of the mixed substances is a diffraction pattern. Furthermore, if the sample contains multiple mixed substances, the same data as described above for each substance can also be stored in the storage unit 16. Alternatively, multiple mixed substances having predetermined weight fractions can be considered as a single mixed substance, and the same data as described above for this single mixed substance can also be stored in the storage unit 16.

[0033] Figure 4 It shows Figure 2 The influence of the object material on the measurement pattern shown. The X-ray scattering pattern y1 shown in this figure... BP It is to Figure 3 The X-ray scattering pattern of the mixed material shown is y x BP_obs Multiply by an appropriate scaling factor S Ck The obtained pattern is from Figure 2 The X-ray scattering pattern of the entire sample shown is y BP_obs The result after subtracting from the middle. Scale factor S Ck The calculation method is described later.

[0034] Figure 5 To represent the X-ray diffraction pattern y1 generated by the crystalline portion of the object material. C . Figure 5 The pattern shown can be obtained from Figure 4Peaks (diffraction lines) can be easily obtained by extracting them from the pattern shown. Furthermore, in the case of a mixture without crystalline substances, Figure 5 The pattern shown can also be found in Figure 2 The pattern shown was obtained directly. Additionally, the X-ray diffraction pattern y1 of the object material... C From 2θ L up to 2θ M (2θ M <2θ T The range was obtained within 2θ. Because X-ray diffraction lines cannot be observed at diffraction angles larger than the aforementioned range, 2θ... M It is a pre-determined diffraction angle.

[0035] In the first embodiment described later, the crystallinity (DOC) of the target substance is... M ) is to Figure 5 The crystal pattern y1 shown C In 2θ L up to 2θ M The integral intensity over the integration range (corrected according to the Lorentz deflection coefficient (Lp correction)) divided by Figure 4 The object material pattern y1 shown BP In 2θ L up to 2θ M This is the value of the integrated intensity over the integration range (after Lp correction and removal of the influence of background intensity).

[0036] Furthermore, in the second embodiment described later, similarly, using Figure 5 The crystal pattern y1 shown C ,as well as Figure 4 The object material pattern y shown BP_obs By using a predetermined recursive successive approximation method, a higher degree of crystallinity (DOC) was obtained than that of the first embodiment.

[0037] Furthermore, in this embodiment, the sample itself, or other samples with the same composition, such as... Figure 6 As shown, the pre-measurement is from 2θ L up to 2θ H X-ray scattering patterns within an angular range. This pattern y0 BP_obs In calculating the above scaling factor S Ck Use when needed.

[0038] (Theoretical background: Crystallinity)

[0039] The theoretical background for calculating crystallinity using the arithmetic device 14 will be explained here. The analysis in the arithmetic device 14 employs a relatively new quantitative analysis method developed by the inventors, which formalizes the crystallinity of the target substance by expressing it as the weight fraction between the crystalline and amorphous portions. Furthermore, using this new quantitative analysis method, the aforementioned proportioning factor S is calculated. Ck The quantitative analysis methods described above are documented in documents such as J. Appl. Cryst. (2016). 49, 1508-1516, Patent No. 6231726, and International Publication No. 2017 / 149913.

[0040] Equation (1) below is the integral intensity Y of each substance derived through the new quantitative analysis method described above. k The relationship is given by K, where K represents the ordinal number of the substance.

[0041]

[0042] Here Y k This is expressed by equation (2). y(2θ) k This is the X-ray scattering pattern of the k-th substance. G(2θ) is the Lp correction factor. The integration range is the full integration range, for example, from 10 degrees of 2θ. L 2θ up to 120 degrees H .

[0043] Y k =∫y(2θ) k G(2θ)d(2θ) (2)

[0044] In addition, a k The reciprocal of N is given by equation (3). Here, N A n is the number of atoms in the chemical formula of substance k. ki M is the number of electrons in the i-th atom contained in the chemical formula of the k-th substance. k It is the chemical formula weight of the kth substance contained in the sample.

[0045]

[0046] Equation (1) can also be expressed as Equation (4).

[0047]

[0048] When the weight ratio of the crystalline portion to the amorphous portion of a substance is defined as the degree of crystallinity, the degree of crystallinity DOC of the k-th substance is expressed by the following formula (5). Here, W kC W is the weight of the crystalline portion of the k-th substance. kA w is the weight of the amorphous portion of the k-th substance. kCis the weight fraction of the crystalline portion in the k-th substance. kA It is the weight fraction of the amorphous portion in the k-th substance.

[0049]

[0050] Let w represent the weight fraction of the k-th substance in the sample. k At that time, w k This is expressed by the following formula (6).

[0051] w k =w kC +w kA (60

[0052] Here, k = 1, and the first substance is taken as the object of crystallinity calculation, i.e., the target substance. Substituting equation (6) into equation (5), and further into equation (4), we obtain the following equation (7) regarding the crystallinity DOC of the first substance. Here, Y 1c The X-ray diffraction pattern y1 originates from the crystalline portion of the first substance. C The Lp-corrected integral intensity (see equation (19)). Y 1A It is the Lp-corrected integral intensity of the X-ray diffraction pattern originating from the amorphous portion of the first material. In both cases, the integration range is the entire range, for example, from 2θ. L up to 2θ H .

[0053]

[0054] According to equation (7), the Lp-corrected integral intensity Y1 of the X-ray scattering pattern of the entire object material and the Lp-corrected integral intensity Y of the X-ray diffraction pattern of the crystalline part of the object material are... 1C If the crystallinity (DOC) is known, then the degree of crystallinity can be calculated.

[0055] (Theoretical background: background strength)

[0056] As mentioned above, the X-ray scattering pattern includes background intensity. The overall X-ray scattering pattern of the k-th material is considered as y(2θ). k BP The background intensity is used as y(2θ). BG The component derived solely from the k-th substance is taken as y(2θ). k If so, then equation (8) holds true.

[0057]

[0058] Here, y(2θ) k BP y(2θ) k and y(2θ)BG The integral strength of each is expressed by equations (9) to (11). These equations hold for any and common integral ranges.

[0059]

[0060] Y k =∫y(2θ) k G(2θ)d(2θ) (10)

[0061] B k =∫y(2θ) BG G(2θ)d(2θ) (11)

[0062] According to equation (8), Y k BP Y k B k It has the following relationship (12).

[0063]

[0064] If the background ratio R of the kth substance is... k By defining it using the following equation (13), equation (12) can be rewritten as equation (14).

[0065] R k =B k / Y k (13)

[0066]

[0067] That is, according to equation (14), the background integral intensity Y k BP and the integral intensity Y without background k Able to utilize background ratio R k Mutual conversion.

[0068] (Theoretical Background: Calculation of Crystallinity DOC (Part 1))

[0069] According to the DD method, the integral intensity Y of the k-th substance is calculated. k BP_calc It is given by the following equation (15).

[0070]

[0071] The integral intensity Y of the k-th substance k BP The integrated intensity Y is considered to be observed through the entire sample. BP_calc With calculation of integral intensity Y k BP_calcThe ratio is obtained, therefore the following equation (16) holds.

[0072]

[0073] Here, Y BP_calc Given by equation (17), D is given by equation (18).

[0074]

[0075]

[0076] That is, the integral intensity Y1 of the first substance as the object of study. BP The integral intensity Y that can be observed based on the entire sample. BP_obs R of all substances in the sample k w k and a k This information can be obtained during sample preparation. Furthermore, Y1 can be calculated using equation (14). BP Converted to Y1. Further, the integral intensity Y of the crystalline portion of the object material. 1C It can be calculated using the following formula (19).

[0077] By obtaining Y1 and Y in this way 1C Substituting into equation (7), we can obtain the crystallinity DOC.

[0078]

[0079] (Theoretical Background: Calculation of Crystallinity DOC (Part 2))

[0080] The crystallinity DOC of equation (7), derived based on the new quantitative analysis method, is calculated by taking the entire range as the integral intensity Y. 1C The integration range of Y1 is a prerequisite for calculation. To calculate these values, it is necessary to accurately identify the X-ray scattering pattern from the crystalline portions contained within the object material. However, the diffraction pattern y1 from the crystalline portions... C Because the diffraction intensity is weak in the high-angle region, it is buried in the scattering patterns from the amorphous portion and other materials, making it difficult to identify. This leads to an underestimation of Y. 1C And crystallinity (DOC).

[0081] Therefore, in order to more accurately calculate the approximate value of crystallinity DOC, the calculation of the integral intensity Y will be considered. 1C The integration range is limited when Y1 is used.

[0082] The overall sample shows an X-ray scattering pattern y(2θ) with a background. BP It is represented by the following equation (20). Here, y(2θ)1BP This is the X-ray scattering pattern of the first substance (the object substance) with a background. y(2θ) k BP It is the X-ray scattering pattern with background of the k-th substance (the mixed substance). Ck It is a scaling factor.

[0083]

[0084] Here, if the y(2θ) of the mixed substance k BP It is known that, according to equations (20) and (16), for k = 2 to K, equation (21) holds. Then, according to the same equation (21), the scaling factor S can be obtained. Ck .

[0085]

[0086] Use the scaling factor S obtained in this way Ck Equation (22) below shows the integral over any range (2θ) X ~2θ Y The integral intensity Y of the object material can be obtained by the following formula (22). XY BP (=Y1 BP ).

[0087]

[0088] For any integration range (2θ) X ~2θ Y The integral intensity Y of the crystalline portion of the object material. C-XY (=Y1 C It can be obtained by the following formula (23).

[0089]

[0090] By substituting these values ​​into equation (7), the crystallinity DOC of the object can be approximately obtained.

[0091] Here, the accuracy of the crystallinity obtained by limiting the integration range is evaluated.

[0092] Figure 7 This indicates that 2θ represents the integral over various ranges. X ~2θ Y The integral intensity Y of the object matter XY Here, X is L, M, or T. Y is M, T, or H. Furthermore, in the following text, Y... C-XY The integral range 2θ is the crystalline portion of the object. X ~2θY The integral intensity in Y. A-XY It is the integral range 2θ over the amorphous part of the object. X ~2θ Y The integral intensity in.

[0093] Based on the above notation, equation (7) can be expressed as equation (24).

[0094]

[0095] Furthermore, by limiting the integration range to 2θ L ~2θ M In this case, crystallinity is expressed as DOC. M DOC M It can be defined as follows (25).

[0096]

[0097] The crystallinity DOC of formula (24) and the crystallinity DOC of formula (25) M The error ΔDOC between M This is expressed by equation (26).

[0098] ΔDOC M =DOC M -DOC (26)

[0099] Equation (26) can be transformed into the following equation (27).

[0100]

[0101] Here, according to the inventor’s research, the value in parentheses on the right side of equation (27) is 0.11.

[0102]

[0103] Furthermore, according to the inventor's research, the part of the following equation (29) on the right side of equation (27) is in 2θ M The value is 0.5 when the temperature is around 70 degrees Celsius.

[0104]

[0105] Therefore, with a crystallinity of 40%, ΔDOCM can be estimated to be 0.0088. This means that as long as other errors are small, equation (30) holds even with limitations on the integration range, i.e., DOC M It is a good approximation of DOC.

[0106] DOC M ≈DOC (30)

[0107] (Theoretical Background: Calculation of Crystallinity DOC (Part 3))

[0108] DOC M It is a good approximation of DOC, when the X-ray scattering pattern of the sample is measured to be greater than 2θ. M A higher angle 2θ T In this case, it can get closer to the true value.

[0109] First, define the initial value DOC as shown in equation (31). T .

[0110]

[0111] The crystallinity DOC of formula (24) and the crystallinity DOC of formula (31) T The error ΔDOC between T This is expressed by the following formula (32).

[0112] ΔDOC T =DOC T -DOC (32)

[0113] ΔDOC T It can be transformed into the following formula (33).

[0114]

[0115] Here, equation (34) is obtained from equation (30), and equation (33) can be transformed as in equation (35).

[0116] DOC≈Y C-LM / Y LM (34)

[0117]

[0118] Due to DOC, DOC T ΔDOC T Given the relationship in equation (36), we can obtain the recursive form of equation (37) using equation (35).

[0119] DOC = DOC T -ΔDOC T (36)

[0120]

[0121] In equation (37), DOC TSubstitute the initial value of DOC on the right side to calculate DOC on the left side. Then, substitute the resulting DOC back into the right side. By repeating this process, a crystallinity DOC close to the true value can be obtained.

[0122] (First Embodiment)

[0123] The first embodiment will now be described. The first embodiment corresponds to the above-described "Calculation of Crystallinity DOC (Part 2)".

[0124] In this embodiment, firstly according to Figure 8 Flowchart for calculating scaling factor S Ck Therefore, the arithmetic unit 14 reads the initial pattern y0 from the storage unit 16. BP _ obs ( Figure 6 (Refer to) (S100).

[0125] Next, the arithmetic unit 14 reads the known pattern y of the mixed substance from the storage unit 16. x BP-obs ( Figure 3 (Refer to S101). Here, the substance being mixed is a type, and k for the substance being mixed is 2.

[0126] In addition, the arithmetic unit 14 reads from the storage unit 16 the chemical formula and chemical formula amount M of each substance constituting the sample (the target substance and the mixed substance). k The number of electrons n in each atom of the substance's chemical formula. ki weight fraction w k and background ratio R k .

[0127] Then, the arithmetic unit 14 calculates the scaling factor S according to equation (21). C2 It is stored in storage unit 16 (S103).

[0128] Next, the arithmetic unit 14 according to Figure 9 Flowchart for calculating crystallinity DOC M To this end, firstly, the arithmetic unit 14 reads the measurement pattern y from the storage unit 16. BP _ obs ( Figure 2 (Refer to S200). Measurement pattern y BP _ obs It is the overall X-ray scattering pattern of the sample, which is measured by X-ray diffraction device 12.

[0129] Next, the arithmetic unit 14 reads the known pattern y of the mixed substance from the storage unit 16. x BP _ obs( Figure 3 (S201). Furthermore, in S103, the calculated scaling factor S is read from the storage unit 16. C2 (S202).

[0130] The arithmetic unit 14 calculates the object material pattern y1 based on the data obtained from S200 to S202. BP (Refer to Figure 4 (S203). Object material pattern y1 BP It is the part of the integrand on the right side of equation (22) excluding the Lp correction factor G(2θ).

[0131] Furthermore, the object material pattern y1 obtained by the computing device 14 from S203 BP 2θ L ~2θ M Diffraction lines were extracted within the angular range to extract the crystal pattern y1. C (Refer to Figure 5 (S204).

[0132] Then, the arithmetic unit 14 calculates the integral intensity Y. LM (S205). Specifically, Y is calculated using equation (22). LM BP Furthermore, the background ratio R1 pre-stored in the storage unit 16 is read (within the integration range 2θ). L ~2θ M The value calculated in the middle), using equation (14) to convert Y LM BP Convert to Y LM Furthermore, the X-ray scattering pattern y1 of the object material BP The data also includes the background intensity shown by the dashed line in the figure, but this information is stored in the storage unit 16. If the X-ray diffraction pattern of the crystallized mixed material, or a crystalline material with a similar composition, is measured beforehand, the background intensity can be easily extracted from it. Furthermore, in the storage unit 16, at 2θ... L ~2θ M The ratio R1 between the integral range and the background involved in the object material is also pre-stored.

[0133] Furthermore, the arithmetic unit 14 processes the crystal pattern y1 obtained in S204. C In 2θ L ~2θ M The integral intensity Y is obtained by integrating the Lp-corrected integral over the angular range. C-LM (S206). Then, the Y obtained in S206 C-LM Divide by Y obtained in S205 LM To obtain crystallinity DOCM (S207). After the above processing, an accurate value of the crystallinity of the target substance can be obtained.

[0134] (Second Implementation)

[0135] The second embodiment will now be described. The first embodiment corresponds to the above-described "Calculation of Crystallinity DOC (Part 3)".

[0136] In this embodiment, the arithmetic unit 14 first calculates according to... Figure 8 Flowchart for calculating scaling factor S Ck This process is the same as in the first embodiment, so the description is omitted here.

[0137] Next, the arithmetic device 14 according to Figure 10 The flowchart calculates the crystallinity DOC. In the same diagram, S300~S306 and… Figure 9 S200 to S206 are the same, so the explanation is omitted here.

[0138] In S307, the arithmetic unit 14 calculates the integral intensity Y. MT Specifically, Y is calculated using equation (22). MT BP Furthermore, the background ratio R1 (in the integration range 2θ) pre-stored in the storage unit 16 is read. M ~2θ T (Calculated from the middle), using formula (14) to calculate Y MT BP Convert to Y MT .

[0139] Next, the arithmetic unit 14 substitutes the values ​​obtained in S305 to S307 into equation (31) to calculate the initial value DOC. T (S308). Then, substitute the values ​​obtained in S305, S307, and S308 into the right side of the recursive formula (37) to obtain the DOC on the left side. Repeat this calculation a predetermined number of times, or until the value of DOC converges, to obtain the final DOC (S309). After the above processing, an accurate value of the crystallinity of the target substance can be obtained.

[0140] This invention is not limited to the embodiments described above, and various modifications can be implemented within the scope of the spirit of this invention, and these modifications are also included within the scope of this invention.

Claims

1. A crystallinity measuring device, characterized in that, include: The measurement pattern acquisition unit acquires the X-ray scattering pattern of the sample being measured, which contains the target substance and other known mixed substances. A known pattern acquisition unit acquires a known X-ray scattering pattern of the mixed material; A crystallization pattern acquisition unit, which, based on the X-ray scattering pattern of the sample, at least partially obtains the X-ray diffraction pattern contained in the crystalline portion of the object material; The crystallization integral intensity calculation unit calculates the integral intensity related to the X-ray diffraction pattern of the crystallized portion. The object material integral intensity calculation unit calculates the integral intensity of the object material with background X-ray scattering pattern based on the X-ray scattering pattern of the sample and the known X-ray scattering pattern, and converts the integral intensity of the object material with background X-ray scattering pattern into the integral intensity of the object material without background X-ray scattering pattern based on the background ratio of the object material. as well as The crystallinity calculation unit calculates the crystallinity of the object material based on the integral intensity related to the X-ray diffraction pattern of the crystalline portion and the integral intensity related to the background-free X-ray scattering pattern of the object material.

2. The crystallinity measuring device according to claim 1, characterized in that, The object material integral intensity calculation unit calculates the integral intensity of the object material related to the background X-ray scattering pattern based on the X-ray scattering pattern of the sample, the known X-ray scattering pattern, the chemical formula weights of the object material and the mixed material, and the number of electrons of each atom belonging to the chemical formulas of the object material and the mixed material.

3. The crystallinity measuring device according to claim 2, characterized in that, The object material integrated intensity calculation unit includes: a unit that subtracts the value obtained by multiplying the integrated intensity related to the known X-ray scattering pattern by a scaling factor from the integrated intensity related to the X-ray scattering pattern of the sample. The scaling factor is calculated based on the chemical formula weights of the target substance and the mixed substance, and the number of electrons of each atom belonging to the chemical formulas of the target substance and the mixed substance.

4. The crystallinity measuring device according to claim 2, characterized in that, The integral intensity calculation unit for the object material calculates the integral intensity using Lorentz bias correction.

5. The crystallinity measuring device according to claim 1, characterized in that, The crystallinity calculation unit uses a successive approximation method based on a predetermined recursive formula to calculate the crystallinity of the target substance.

6. The crystallinity measuring device according to claim 5, characterized in that, The predetermined recursive formula is: DOC=DOC T +DOC×(Y MT / AND LM +And MT ), DOC is the degree of crystallinity of the substance in question. Y LM It is the integrated intensity related to the X-ray scattering pattern of the object material, with the integration range from the first diffraction angle to the second diffraction angle. Y MT It is the integrated intensity related to the X-ray scattering pattern of the object material, taking the period from the second diffraction angle to the third diffraction angle as the integration range. DOC T As shown in the following formula, DOC T =Y C-LM / (AND LM +And MT ) Y C-LM It is the integrated intensity related to the X-ray scattering pattern of the crystalline portion, with the first diffraction angle to the second diffraction angle as the integration range.

7. A method for measuring crystallinity, characterized in that, include: The measurement pattern acquisition step acquires the X-ray scattering pattern of the sample being measured, which contains the target substance and other known mixed substances; The known pattern acquisition step acquires a known X-ray scattering pattern of the mixed material; The crystallization pattern acquisition step, based on the X-ray scattering pattern of the sample, at least partially obtains the X-ray diffraction pattern contained in the crystalline portion of the object material; The crystallization integral intensity calculation step calculates the integral intensity related to the X-ray diffraction pattern of the crystalline portion. The integral intensity calculation step for the target material involves calculating the integral intensity related to the X-ray scattering pattern of the target material with background based on the X-ray scattering pattern of the sample and the known X-ray scattering pattern, and converting the integral intensity related to the X-ray scattering pattern of the target material with background to the integral intensity related to the X-ray scattering pattern of the target material without background based on the background ratio of the target material. as well as The crystallinity calculation step calculates the crystallinity of the object material based on the integral intensity related to the X-ray diffraction pattern of the crystalline portion and the integral intensity related to the background-free X-ray scattering pattern of the object material.

8. An information storage medium, which is a computer-readable information storage medium, characterized in that, It stores programs for causing the computer to perform the following steps: The measurement pattern acquisition step involves acquiring an X-ray scattering pattern of a sample containing the object being measured and other known mixed substances. The known pattern acquisition step acquires a known X-ray scattering pattern of the known mixed material; The crystallization pattern acquisition step, based on the X-ray scattering pattern of the sample, at least partially obtains the X-ray diffraction pattern contained in the crystalline portion of the object material; The crystallization integral intensity calculation step calculates the integral intensity related to the X-ray diffraction pattern of the crystalline portion. The integral intensity calculation step for the target material involves calculating the integral intensity related to the X-ray scattering pattern of the target material with background based on the X-ray scattering pattern of the sample and the known X-ray scattering pattern, and converting the integral intensity related to the X-ray scattering pattern of the target material with background to the integral intensity related to the X-ray scattering pattern of the target material without background based on the background ratio of the target material. as well as The crystallinity calculation step calculates the crystallinity of the object material based on the integral intensity related to the X-ray diffraction pattern of the crystalline portion and the integral intensity related to the background-free X-ray scattering pattern of the object material.

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