Crystallinity degree measurement device, crystallinity degree measurement method and program

Abstract

To more accurately measure a degree of crystallinity of a target substance, taking deterioration in crystallinity of a crystalline portion of the target substance into consideration.SOLUTION: A crystallinity degree measurement device 10 includes: an X-ray scattering pattern acquisition unit 101 that acquires an X-ray scattering pattern of a sample including a crystalline portion and an amorphous portion of a target substance; a pattern decomposition unit 102 that acquires a diffraction pattern and a continuous pattern of the crystalline portion from the X-ray scattering pattern; a target-substance intensity calculation unit 103 that calculates an integrated intensity of the target substance, based on the X-ray scattering pattern and chemical formula information of the target substance; a target-substance pattern calculation unit 104 that calculates, from the continuous pattern, a scattering pattern of the target substance including the crystalline portion and the amorphous portion; and a structural disorder parameter determination unit 105 that determines a structural disorder parameter of the crystalline portion, based on the diffraction pattern of the crystalline portion and the scattering pattern of the target substance.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] The present invention relates to a crystallinity measurement device, a crystallinity measurement method, and a program, and in particular to measurement of crystallinity using X-ray diffraction. [Background technology]

[0002] There are crystalline and amorphous polymers in polymers, but even crystalline polymers do not have a crystalline structure entirely; they contain a mixture of crystalline and amorphous parts. The ratio of the weight of the crystalline part to the total weight of a crystalline polymer is called the degree of crystallinity. The degree of crystallinity is important information for understanding the properties of crystalline polymers, such as their mechanical and chemical properties.

[0003] Among the various methods for measuring crystallinity, the method using X-ray diffraction has great practical advantages, such as the fact that, in principle, the size of the sample is not important and that the method can be performed non-destructively. Summary of the Invention [Problem to be solved by the invention]

[0004] In methods using X-ray diffraction, it is known that the crystallinity of a target substance is determined by dividing the integrated intensity of the scattering pattern (in this case, the diffraction pattern) from the crystalline portion of the target substance by the sum of the integrated intensities of the scattering patterns from the crystalline portion and the amorphous portion (i.e., the integrated intensity of the scattering pattern of the entire target substance).

[0005] Therefore, in order to calculate the degree of crystallinity, it is necessary to accurately extract the diffraction pattern from at least the crystalline portion from the entire observed pattern. However, even if the target substance is a crystalline portion, its crystallinity is thought to be actually low. Therefore, the intensity of the diffraction pattern of the crystalline portion of the target substance is observed to be lower than the actual intensity, and the degree of crystallinity of the target substance is thought to be calculated to be lower than the actual intensity.

[0006] The present invention has been made in consideration of the above-mentioned problems, and its object is to provide a crystallinity measurement device, a crystallinity measurement method, and a program that can more accurately measure the crystallinity of a target substance, taking into account the decrease in crystallinity of the crystalline portion of the target substance. [Means for solving the problem]

[0007] (1) In order to solve the above problem, the crystallinity measuring device of the present invention includes an X-ray scattering pattern acquisition means for acquiring an X-ray scattering pattern of a sample including a crystalline portion and an amorphous portion of a target substance; a pattern decomposition means for acquiring a diffraction pattern of the crystalline portion and a continuous pattern from the X-ray scattering pattern; a target substance intensity calculation means for calculating an integrated intensity relating to the target substance based on the X-ray scattering pattern and chemical formula information of the target substance; a target substance pattern calculation means for calculating a scattering pattern of the target substance including the crystalline portion and the amorphous portion from the continuous pattern such that its integrated intensity matches the integrated intensity calculated by the target substance intensity calculation means; a structural irregularity parameter determination means for determining a structural irregularity parameter of the crystalline portion based on the diffraction pattern of the crystalline portion and the scattering pattern of the target substance; and a crystallinity output means for outputting the crystallinity of the target substance calculated in accordance with the determined structural irregularity parameter.

[0008] (2) In the crystallization measurement apparatus described in (1), the structural irregularity parameter determination means may include a provisional crystallinity calculation means for calculating a provisional crystallinity, the provisional crystallinity being a numerator obtained by integrating a correction pattern obtained by multiplying the diffraction pattern of the crystalline portion by a structural irregularity factor including the structural irregularity parameter over a given integration range, and a denominator obtained by integrating a scattering pattern of the target substance over the given integration range, for each of the plurality of structural irregularity factors, while changing the given integration range; and a parameter selection means for calculating an evaluation value for each of the plurality of structural irregularity parameters by substituting the plurality of provisional crystallinity values ​​calculated while changing the given integration range into a predetermined evaluation formula, and selecting one of the structural irregularity parameters based on the evaluation value.

[0009] (3) In the crystallinity measuring apparatus described in (2), the structural disorder factor may be given by the following formula: where λ is the wavelength of the incident X-ray, and k is the structural disorder parameter.

[0010]

number

[0011] (4) In the crystallinity measurement apparatus described in (3), the evaluation value may be expressed by the following formula S, where f n is the tentative crystallinity index for the nth integration range, and D0 is a fitting parameter.

[0012]

number

[0013] (5) In the crystallinity measurement device according to any one of (1) to (4), the sample may contain one or more crystalline fillers. The pattern decomposition means may acquire a diffraction pattern of the one or more crystalline fillers from the X-ray scattering pattern. The target substance intensity calculation means may include a crystalline filler intensity calculation means for calculating an integrated intensity of a diffraction pattern of one of the crystalline fillers. The integrated intensity of the target substance may be calculated by multiplying the integrated intensity of the one crystalline filler by a ratio according to chemical formula information of the crystalline filler and the target substance contained in the sample.

[0014] (6) In the crystallinity measuring apparatus described in (5), the sample may contain one or more non-crystalline fillers.

[0015] (7) In the crystallinity measuring apparatus according to any one of (1) to (6), the continuous pattern may include a background. The target substance pattern calculating means may include a background subtracting means for subtracting the background from the continuous pattern.

[0016] (8) In the crystallinity measurement apparatus described in (7), the background subtraction means may include: a background intensity calculation means that calculates an integrated intensity of the background based on an integrated intensity of an X-ray scattering pattern of the sample and chemical formula information of a substance contained in the sample; and a background calculation means that calculates the background such that its integrated intensity coincides with the integrated intensity calculated by the background intensity calculation means.

[0017] In the crystallization measuring apparatus described in (9) (7) or (8), the target substance pattern calculation means may calculate a scattering pattern of the target substance by multiplying the continuous pattern from which the background has been subtracted by a ratio corresponding to the integrated intensity calculated by the target substance intensity calculation means.

[0018] (10) The crystallinity measurement method of the present invention includes an X-ray scattering pattern acquisition step of acquiring an X-ray scattering pattern of a sample including a crystalline portion and an amorphous portion of a target substance; a pattern decomposition step of acquiring a diffraction pattern of the crystalline portion and a continuous pattern from the X-ray scattering pattern; a target substance intensity calculation step of calculating an integrated intensity for the target substance based on the X-ray scattering pattern and chemical formula information of the target substance; a target substance pattern calculation step of calculating a scattering pattern of the target substance including the crystalline portion and the amorphous portion from the continuous pattern such that its integrated intensity matches the integrated intensity calculated by the target substance intensity calculation means; a structural irregularity parameter determination step of determining a structural irregularity parameter of the crystalline portion based on the diffraction pattern of the crystalline portion and the scattering pattern of the target substance; and a crystallinity output step of outputting the crystallinity of the target substance calculated in accordance with the determined structural irregularity parameter.

[0019] (11) A program according to the present invention is a program for operating a computer as an X-ray scattering pattern acquisition means for acquiring an X-ray scattering pattern of a sample including a crystalline portion and an amorphous portion of a target substance, a pattern decomposition means for acquiring a diffraction pattern of the crystalline portion and a continuous pattern from the X-ray scattering pattern, a target substance intensity calculation means for calculating an integrated intensity of the target substance based on the X-ray scattering pattern and chemical formula information of the target substance, a target substance pattern calculation means for calculating a scattering pattern of the target substance including the crystalline portion and the amorphous portion from the continuous pattern such that the integrated intensity of the scattering pattern coincides with the integrated intensity calculated by the target substance intensity calculation means, a structural irregularity parameter determination means for determining a structural irregularity parameter of the crystalline portion based on the diffraction pattern of the crystalline portion and the scattering pattern of the target substance, and a crystallinity output means for outputting a crystallinity of the target substance calculated according to the determined structural irregularity parameter. This program may be stored in a computer-readable information storage medium. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 is a configuration diagram of a crystallinity measuring device according to an embodiment of the present invention. [Figure 2A] FIG. 1 is a diagram illustrating an example of an observation pattern of a sample. [Figure 2B] FIG. 2 is a diagram showing a schematic diagram of a diffraction pattern of a crystalline portion of a target substance. [Figure 2C] FIG. 2 is a diagram illustrating an example of a diffraction pattern of a crystalline filler. [Figure 2D] FIG. 1 is a diagram illustrating an example of a continuous pattern. [Figure 3A] FIG. 2 is a diagram showing a schematic example of an X-ray scattering pattern of a sample in the case where the entire target substance is amorphous. [Figure 3B] FIG. 3B is a schematic diagram showing a reference continuous pattern created based on the X-ray scattering pattern shown in FIG. 3A. [Figure 4] FIG. 1 is a functional block diagram of a crystallinity measurement device according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings.

[0022] Fig. 1 is a diagram showing the configuration of a crystallinity measurement apparatus according to one embodiment of the present invention. As shown in the figure, the crystallinity measurement apparatus 10 includes an X-ray diffraction apparatus 12, a calculation device 14, a storage unit 16, and a display unit 18. When calculating the crystallinity based on an observation pattern obtained from another X-ray diffraction apparatus, the crystallinity measurement apparatus 10 does not need to include the X-ray diffraction apparatus 12. In this case, the crystallinity measurement apparatus 10 may be composed of the calculation device 14, the storage unit 16, and the display unit 18, and the observation pattern obtained from the other X-ray diffraction apparatus is stored in advance in the storage unit 16.

[0023] The X-ray diffraction device 12 performs X-ray diffraction measurement. Specifically, the X-ray diffraction device 12 irradiates an X-ray of a known wavelength onto a sample and measures the intensity of the scattered X-ray. Data on the X-ray intensity for each value of the diffraction angle 2θ is output from the X-ray diffraction device 12 to the calculation device 14 as an observation pattern. Note that the observation pattern output to the calculation device 14 may be corrected using the Lorentz polarization factor (Lp correction). The X-ray diffraction device 12 measures the intensity of the scattered X-ray at a sufficiently small minimum angle 2θ of about 10 degrees. L Therefore, the maximum angle 2θ is sufficiently large, about 120 degrees. H It is possible to measure the intensity of the scattered X-rays at each diffraction angle up to 1000 nm. In this specification, the X-ray intensity profile (data showing the change in X-ray intensity with respect to the change in diffraction angle) measured by the X-ray diffraction device 12 is referred to as the "X-ray scattering pattern" or "observation pattern." When the sample is crystalline, the X-ray scattering pattern is particularly called the "X-ray diffraction pattern."

[0024] In this embodiment, the sample to be measured for the X-ray scattering pattern includes a target substance such as a powder or flowable polymer, some of which may be in a crystalline state and the rest in an amorphous state. One or more fillers are mixed into the sample. When the sample is prepared, the types and weight ratios of the substances that make up the sample are known. The chemical formula and chemical formula weight of each substance are also known.

[0025] In the following, as an example, the sample is assumed to be in bulk solid form. When such a sample is synthesized, a powder or a polymer having fluidity is mixed with a number of fillers, etc. This mixture is then molded and heated to produce the resin material of the sample product. It is needless to say that the present invention can be applied not only to bulk solid samples, but also to powder samples.

[0026] As an example of such a sample, the crystallinity measurement of a sample whose target substance is PPS (Poly Phenylene Sulfide) resin, known as a high performance engineering resin, is taken below. This sample is mixed with calcium carbonate (CaCO3) as a crystalline filler and E-glass fiber as a non-crystalline filler. However, the present invention may be applied to the crystallinity measurement of various target substances in various samples other than the above sample. For example, crystalline filler and non-crystalline filler do not need to be mixed into the sample. Alternatively, multiple types of crystalline fillers may be mixed into the sample. Similarly, multiple types of non-crystalline fillers may be mixed into the sample.

[0027] The arithmetic device 14 is configured, for example, by a known computer system, and includes a CPU and a memory. A storage unit 16 configured by a computer-readable information storage medium such as an SSD (Solid State Disk) or an HDD (Hard Drive Disk) is connected to the arithmetic device 14. A crystallinity measurement program according to an embodiment of the present invention is stored in the storage unit 16, and the device and method according to an embodiment of the present invention are realized by the arithmetic device 14 executing this program. The storage unit 16 further stores chemical formula information (chemical formula, chemical formula weight, number of electrons of each atom contained in the substance) of each substance contained in the sample, and weight ratios of each substance.

[0028] The display unit 18 is a display device that displays the results of the calculations performed by the arithmetic unit 14. For example, the display unit 18 displays the crystallinity of the target substance using numerical values ​​or a graph.

[0029] Here, we will explain the procedure for calculating the crystallinity using the crystallinity measurement apparatus 10. The calculation of the crystallinity is broadly divided into (1) pattern decomposition, (2) calculation of structural disorder parameters, (3) calculation of the integrated intensity of the patterns derived from each component, and (4) calculation of the pattern of the entire target material (PPS).

[0030] (1) Pattern decomposition: Observation pattern y(2θ) which is the X-ray scattering pattern of the sample from the X-ray diffraction device 12 Total_obs Once we obtain the pattern y(2θ), we decompose it into multiple patterns. Figure 2A shows the observed pattern y(2θ) Total_obs As shown in the figure, the observation pattern y(2θ) Total_obs contains many peaks derived from one or more crystalline components and a gentle continuous pattern. As described above, the sample contains crystalline and amorphous parts of PPS, calcium carbonate as a crystalline filler, and E-glass fiber as a non-crystalline filler. Therefore, the observed pattern y(2θ) Total_obs The diffraction pattern y(2θ) of the crystalline part of PPS P_C and the diffraction pattern y(2θ) of the crystalline filler CFand continuous pattern y(2θ) H It can be broken down into:

[0031]

number

[0032] FIG. 2B shows the diffraction pattern y(2θ) of the crystalline part of PPS. P_C FIG. 2C shows the diffraction pattern y(2θ) of the crystalline filler. CF FIG. 2D shows a schematic diagram of a continuous pattern y(2θ) H is shown diagrammatically.

[0033] In the pattern decomposition, for example, the Rietveld method or the Whole-Powder-Pattern Decomposition (WPPD) method or other Whole-Powder-Pattern Fitting (WPPF) method is used. In this case, the pattern y(2θ) P_C and pattern y(2θ) CF The patterns are identified based on the lattice constants and other crystal structure information (structural parameters) of PPS and calcium carbonate.

[0034] Continuous pattern y(2θ) H For the known reference continuous pattern y(2θ) H 100 Based on this, the pattern is identified. That is, the continuous pattern y(2θ) H is assumed to be as shown in the following equation (2): where Sc is a scale factor that is a variable parameter, and a(2θ) is an auxiliary function that includes a variable parameter. This auxiliary function is a polynomial or other function whose shape can be changed by the variable parameter.

[0035]

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[0036] By substituting equation (2) into equation (1), the observed pattern y(2θ) Total_obs can be expressed as the following equation (3).

[0037]

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[0038] Reference continuous pattern y(2θ) H 100 is based on the X-ray scattering pattern measured after the sample was sufficiently melted at high temperature in advance to completely amorphize the PPS. Figure 3A shows the X-ray scattering pattern of a sample in which the PPS has been completely amorphized in this way. The pattern contains peaks due to the crystalline filler, so by removing these peaks, the reference continuous pattern y(2θ) shown in Figure 3B can be obtained. H 100 The reference continuous pattern y(2θ) can be obtained. H 100 The continuous pattern y(2θ) includes a continuous pattern due to the amorphous part of PPS, a continuous pattern due to the amorphous filler, and a background. H Therefore, in this embodiment, the continuous pattern y(2θ) is calculated by fitting a scale factor Sc to be multiplied by the reference continuous pattern and an auxiliary function a(2θ). H I try to get it.

[0039] The pattern y(2θ) obtained as above P_C and pattern y(2θ) CF may be corrected by equations (4) and (5). Equations (4) and (5) are used to calculate the observed pattern y(2θ) Total_obs From the continuous pattern y(2θ) H The value obtained by subtracting y(2θ) P_C and y(2θ) CF By dividing proportionally by the value of y(2θ) CF obs and y(2θ) P_C obsThese values ​​are calculated as y(2θ) P_C and y(2θ) CF If used instead of , the degree of crystallinity DOC can be determined more accurately.

[0040]

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[0041]

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[0042] (2) Calculation of structural disorder parameters: The degree of crystallinity DOC is expressed by the following formula (6). P_C is the weight ratio of the crystalline part of PPC, and w P_NC is the weight ratio of the amorphous part of PPC.

[0043]

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[0044] When a sample contains K types of substances, the integrated intensity Y k and the weight ratio of the same substance w k The relationship between and has the following formula (7). This relationship is explained in, for example, J. Appl. Cryst. (2016). 49, 1508-1516, Japanese Patent No. 6231726, and International Publication WO 2017 / 149913. Note that the integral intensity Y k When calculating, the scattering pattern of the kth material is multiplied by the Lp correction factor as the integrand function. The integral range is the entire range, for example, 2θ of about 10 degrees. L 2θ of about 120 degrees H That is until now.

[0045]

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[0046] Here, a k The reciprocal of N is given by the following equation (8). k A is the number of atoms in the chemical formula of the kth substance. ki is the number of electrons in the i-th atom in the chemical formula of the k-th substance. k is the formula weight of the kth substance contained in the sample. k A , number of electrons n ki , formula weight M k is referred to as chemical formula information in this specification.

[0047]

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[0048] From the formulas (7) and (6), the degree of crystallinity DOC is expressed by the following formula (9): P_C is the integrated intensity of the crystalline part of the PPC, and Y P_NC is the integrated intensity of the amorphous part of PPC, and Y P is the integrated intensity over the PPC.

[0049]

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[0050] By the way, in a material such as PPS, which has a mixture of crystalline and amorphous parts, the crystallinity of the crystalline parts is thought to be low. Therefore, y(2θ) P_C It is considered that the observed value is lower than the actual value. Therefore, as shown in the following equation (10), the correction pattern y(2θ) P_C D The corrected integral intensity is then used as the numerator of equation (9) to obtain a more accurate degree of crystallinity DOC.

[0051]

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[0052] Here, the correction pattern y(2θ) P_C D is the original pattern y(2θ) P_C is multiplied by the structural disorder factor shown in the following formula (11).

[0053]

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[0054] In formula (11), λ is the wavelength of the incident X-ray, and k is the structural disorder parameter. The structural disorder parameter k indicates the degree of crystallinity reduction and is determined as follows:

[0055] In other words, the integration range is 2θ L From 2θ n The partial integrated intensity of the crystalline portion of the PPS is calculated by formula (12). The partial integrated intensity of the entire PPS is calculated by formula (13). Here, 2θ n is the diffraction angle that is the upper limit of the integral range, and indicates the nth angle when the range from about 60 degrees to about 120 degrees is divided into N. Also, G(2θ) is the Lp correction factor. "Partial integrated intensity" means the intensity obtained by integrating a part of the integral range. Among the integrands in equation (13), y(2θ) which indicates the scattering pattern of the entire PPS P The method for calculating this will be described later.

[0056]

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[0057]

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[0058] Then, using equations (12) and (13), the provisional crystallinity f is calculated as shown in equations (14) and (15). n Define.

[0059]

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[0060]

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[0061] This tentative crystallinity f n As the value of n increases, it is believed that the value of the true degree of crystallinity fluctuates around the value, eventually converging to the value of the true degree of crystallinity. This is because large peaks that have a large effect on the integrated intensity value are present at intervals in the low angle region. Therefore, when the evaluation value S shown in the following formula (16) is minimized, the value of the structural disorder parameter k is considered to be accurate. Here, D0 is a fitting (variable) parameter, and when fitting is completed, it becomes a value close to the true degree of crystallinity.

[0062]

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[0063] In this embodiment, the value of the evaluation value S is calculated multiple times while changing the pair of the structural irregularity parameter k and the parameter D0, and the structural irregularity parameter k that gives the smallest evaluation value S is identified. In this process, for example, the Nelder-Mead method (simplex method / amoeba method), which is a type of optimization algorithm, may be used. Once the value of the structural irregularity parameter k is identified, the value of K is used to calculate 2θ L From 2θ H The integral range is set to and the true degree of crystallinity DOC is calculated using formula (14). Alternatively, the value of D0 may be taken as the true degree of crystallinity DOC.

[0064] (3) Calculation of the integrated intensity of each component in the sample: Among the integrand functions in the above equation (13), y(2θ) which shows the scattering pattern of the entire PPS P To obtain the integral intensity of each component in the sample,

[0065] First, the observed pattern y(2θ) Total_obs The integral intensity Y Total_obs is calculated using the following equation (17).

[0066]

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[0067] Furthermore, the diffraction pattern y(2θ) of the crystalline filler CF The integral intensity Y CF is calculated using the following equation (18).

[0068]

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[0069] Next, equation (7) can be transformed to obtain the following equation (19). This gives the sum of the integrated intensities of all substances contained in the sample, Y Total is the integrated intensity of a single material, Y CF This can be derived from (Equation (18)).

[0070]

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[0071] Therefore, by substituting equations (17) and (19) into the following equation (20), the integrated intensity of the background B P can be sought.

[0072]

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[0073] Furthermore, by transforming equation (7), we can obtain the following equation (21). This gives the integral intensity Y P For the integral intensity of a single material, Y CF It can be derived from

[0074]

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[0075] (4) Scattering pattern y(2θ) of the entire PPS P Calculation of the scattering pattern y(2θ) of the entire PPS P The continuous pattern y(2θ) H As a prerequisite, the background pattern b(2θ) P Here, the known alpha-SiO2 background pattern b(2θ) is calculated using the following equation (22): Si By scaling the background pattern b(2θ) P get.

[0076]

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[0077] Here, B Si can be calculated using the following equation (23).

[0078]

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[0079] The background pattern of alpha-SiO2 is b(2θ) Si The reason for the selection was that the a calculated for the average chemical composition of the entire sample in this embodiment k and a calculated for alpha-SiO2 k This is because the values ​​of are close to each other.

[0080] Next, using equation (24), the background pattern b(2θ) P The continuous pattern y(2θ) H The corrected continuous pattern y(2θ) is subtracted from H_NC get.

[0081]

number

[0082] This pattern y(2θ) H_NC contains a pattern derived from the amorphous portion of PPS and a pattern derived from the amorphous filler. There is no significant difference in shape between the pattern derived from the amorphous portion of PPS and the pattern derived from the amorphous filler. In addition, the scattering pattern y(2θ) of the entire PPS P is simply integrated using equation (13) and used in the calculation. Therefore, the corrected continuous pattern y(2θ) is calculated using the following equation (24): H_NC By scaling, the pattern y(2θ) of the entire PPS P get.

[0083]

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[0084] where the integral intensity Y H_NC can be calculated using the following equation (26).

[0085]

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[0086] From the above, the scattering pattern y(2θ) of the entire PPS is P can be obtained, and the structural disorder parameter k can be calculated. The calculated k can then be used to obtain a more accurate crystallinity DOC.

[0087] Here, the details of the crystallinity measurement device 10 will be described. FIG. 4 is a functional block diagram of the crystallinity measurement device 10. As shown in the figure, the crystallinity measurement device 10 functionally includes an observation pattern acquisition unit 101, a pattern decomposition unit 102, a target substance intensity calculation unit 103, a target substance pattern calculation unit 104, a structural disorder parameter determination unit 105, and a crystallinity output unit 106. The pattern decomposition unit 102 includes a pattern recalculation unit 102a. The target substance intensity calculation unit 103 includes a crystalline filler intensity calculation unit 103a. The target substance pattern calculation unit 104 includes a background subtraction unit 104a, and the background subtraction unit 104a includes a background intensity calculation unit 104b and a background calculation unit 104c. In addition, the structural disorder parameter determination unit 105 includes a tentative crystallinity calculation unit 105a and a parameter selection unit 105b. These functions are realized by executing the above-mentioned crystallinity measurement program on the arithmetic device 14, which is a computer system.

[0088] The observation pattern acquisition unit 101 acquires an observation pattern y(2θ) which is an X-ray scattering pattern of a sample from the X-ray diffraction device 12. Total_obs Get the.

[0089] The pattern decomposition unit 102 uses a full pattern fitting method to obtain the observed pattern y(2θ) Total_obs The diffraction pattern y(2θ) of the crystalline part of PPS P_C and the pattern y(2θ) due to the crystalline filler CF and continuous pattern y(2θ) H The pattern decomposition unit 102 decomposes the pattern y(2θ) P_C and pattern y(2θ) CF The patterns are identified based on the structural parameters of PPS and calcium carbonate. H For the reference continuous pattern y(2θ) H 100 Based on this, the pattern is identified.

[0090] The pattern decomposition unit 102 includes a pattern recalculation unit 102a. The pattern recalculation unit 102a calculates y(2θ) from equations (4) and (5). CF obs and y(2θ) P_C obs The observed pattern y(2θ) Total_obs In the subsequent processing, the y(2θ) obtained by pattern decomposition is used. CF and y(2θ) P_C Instead of y(2θ) CF obs and y(2θ) P_C obs is used.

[0091] The target substance intensity calculation unit 103 calculates an integrated intensity Y P The crystalline filler intensity calculation unit 103a of the target substance intensity calculation unit 103 calculates the observation pattern y(2θ) Total_obs Diffraction pattern y(2θ) of crystalline filler obtained from CF is given from the pattern decomposition unit 102. The crystalline filler intensity calculation unit 103a calculates the integrated intensity Y CF The target substance intensity calculation unit 103 calculates the integrated intensity Y CF The integral intensity Y P Specifically, the integral intensity Y is calculated using equation (21). P Calculate.

[0092] The target material pattern calculation unit 104 calculates the scattering pattern y(2θ) of the entire PPS (including the crystalline and amorphous parts). P The integral intensity is Y P The continuous pattern y(2θ) is made to match H It is calculated from.

[0093] The background subtraction unit 104a of the target material pattern calculation unit 104 calculates the continuous pattern y(2θ) corrected by the formula (24). H_NC At this time, the background intensity calculation unit 104b obtains the background b(2θ) P The integral intensity of B P is the integrated intensity y(2θ) of the X-ray scattering pattern of the sample. Total_obs and the chemical formula information of the substances contained in the sample (PPS, calcium carbonate, and E-glass fiber). P Then, the background calculation unit 104c calculates the background b(2θ) P The integrated intensity B P Specifically, the reference background b(2θ) is calculated so that it coincides with the reference background b(2θ) Si Using the above, the background b(2θ) is calculated by equation (22). P Calculate.

[0094] The target material pattern calculation unit 104 calculates the corrected continuous pattern y(2θ) H_NC With respect to the integrated intensity Y P By multiplying the ratio according to P Specifically, y(2θ) is calculated using equation (25). P Calculate.

[0095] The structural disorder parameter determination unit 105 determines the diffraction pattern y(2θ) of the crystalline portion of PPS. P_C and the scattering pattern y(2θ) of the entire PPS P The tentative crystallinity calculation unit 105a determines the structural disorder parameter k of the crystalline portion of the PPS based on the formulas (14) and (15). n Calculate.

[0096] The tentative crystallinity calculation unit 105a calculates the tentative crystallinity f n(1 to N) and the evaluation value S shown in formula (16). The parameter selection unit 105b selects a pair of values ​​of the structural disorder parameter k and the parameter D0 that results in a small evaluation value S.

[0097] The crystallinity output unit 106 outputs the crystallinity according to the structural disorder parameter k selected by the parameter selection unit 105b as the true crystallinity DOC. The crystallinity output unit 106 outputs the crystallinity DOC by displaying it on the display unit 18, for example.

[0098] According to the crystallinity measurement apparatus 10 described above, the structural disorder parameter k can be appropriately determined, and a more accurate crystallinity DOC can be obtained using the determined structural disorder parameter k.

[0099] The present invention is not limited to the above-described embodiment, but various modifications are possible, and such modifications also fall within the scope of the present invention.

[0100] For example, in the above embodiment, the integrated intensity Y P is the integral intensity Y of the crystalline filler. CF (Equation (21)). In addition, the integrated intensity of the background B P If is known, the integrated intensity Y of the observed pattern can be calculated by equation (20). Total_obs from the integral intensity Y Total (Equation (20)), and the integrated intensity Y Total The integral intensity Y of the target substance PPS P It is possible to calculate the integrated intensity of all materials, including

[0101] In the above embodiment, the corrected continuous pattern y(2θ) H_NC Scaling to y(2θ) P In addition, the continuous pattern y(2θ) H_NC By scaling, the pattern y(2θ) of the amorphous part of PPS is obtained. P_NC The pattern y(2θ) P_NC and y(2θ)P_C By adding, y(2θ) P may be obtained.

Claims

1. An X-ray scattering pattern acquisition means for acquiring an X-ray scattering pattern of a sample including a crystalline portion and an amorphous portion of a target substance; A pattern decomposition means for obtaining a diffraction pattern of the crystalline portion and a continuous pattern from the X-ray scattering pattern; a target substance intensity calculation means for calculating an integrated intensity relating to the target substance based on the X-ray scattering pattern and chemical formula information of the target substance; a target substance pattern calculation means for calculating a scattering pattern of the target substance including the crystalline portion and the amorphous portion from the continuous pattern such that the integrated intensity of the scattering pattern coincides with the integrated intensity calculated by the target substance intensity calculation means; a structural disorder parameter determining means for determining a structural disorder parameter of the crystalline portion based on a diffraction pattern of the crystalline portion and a scattering pattern of the target substance; a crystallinity output means for outputting the crystallinity of the target substance calculated according to the determined structural irregularity parameter; A crystallinity measuring apparatus comprising:

2. The crystallinity measuring apparatus according to claim 1, The structural irregularity parameter determining means comprises: a tentative crystallinity calculation means for calculating a tentative crystallinity having a numerator obtained by integrating a correction pattern obtained by multiplying the diffraction pattern of the crystalline portion by a structural disorder factor including the structural disorder parameter over a given integration range and a denominator obtained by integrating a scattering pattern of the target substance over the given integration range for each of a plurality of structural disorder factors while changing the given integration range; a parameter selection means for calculating an evaluation value for each of the plurality of structural irregularity parameters by substituting the plurality of tentative crystallinity degrees, which are calculated while changing the given integral range, into a predetermined evaluation formula, and selecting one of the structural irregularity parameters based on the evaluation value; A crystallinity measuring apparatus comprising:

3. The crystallinity measuring apparatus according to claim 2, The structural disorder factor is given by the following formula, where λ is the wavelength of the incident X-ray, and k is the structural disorder parameter. [0010]

4. The crystallinity measuring apparatus according to claim 3, The evaluation value is expressed by the following formula S, where fn is the tentative crystallinity relating to the n-th integral range, and D0 is a fitting parameter. [0025]

5. The crystallinity measuring apparatus according to claim 1, The sample comprises one or more crystalline fillers; The pattern decomposition means obtains a diffraction pattern of the one or more crystalline fillers from the X-ray scattering pattern, The target substance intensity calculation means a crystalline filler intensity calculation means for calculating an integrated intensity of a diffraction pattern of the crystalline filler of Calculating an integrated intensity related to the target substance by multiplying the integrated intensity related to the crystalline filler of the first embodiment by a ratio according to chemical formula information of the crystalline filler and the target substance contained in the sample; Crystallinity measuring device.

6. The crystallinity measuring apparatus according to claim 5, The sample includes one or more non-crystalline fillers.

7. The crystallinity measuring apparatus according to claim 1, the continuous pattern includes a background; The object substance pattern calculation means includes background subtraction means for subtracting the background from the continuous pattern.

8. The crystallinity measuring apparatus according to claim 7, The background subtraction means a background intensity calculation means for calculating an integrated intensity of the background based on an integrated intensity of an X-ray scattering pattern of the sample and chemical formula information of a substance contained in the sample; a background calculation means for calculating the background so that its integrated intensity coincides with the integrated intensity calculated by the background intensity calculation means; A crystallinity measuring apparatus comprising:

9. The crystallinity measuring apparatus according to claim 7 or 8, A crystallinity measurement device in which the target substance pattern calculation means calculates the scattering pattern of the target substance by multiplying the continuous pattern from which the background has been subtracted by a ratio corresponding to the integrated intensity calculated by the target substance intensity calculation means.

10. An X-ray scattering pattern acquisition step of acquiring an X-ray scattering pattern of a sample including a crystalline portion and an amorphous portion of a target substance; A pattern decomposition step of obtaining a diffraction pattern of the crystalline portion and a continuous pattern from the X-ray scattering pattern; a target substance intensity calculation step of calculating an integrated intensity relating to the target substance based on the X-ray scattering pattern and chemical formula information of the target substance; a target substance pattern calculation step of calculating a scattering pattern of the target substance including the crystalline portion and the amorphous portion from the continuous pattern such that the integrated intensity of the scattering pattern coincides with the integrated intensity calculated in the target substance intensity calculation step; a structural imperfection parameter determining step of determining a structural imperfection parameter of the crystalline portion based on a diffraction pattern of the crystalline portion and a scattering pattern of the target substance; a crystallinity output step of outputting the crystallinity of the target substance calculated according to the determined structural irregularity parameter; A method for measuring crystallinity comprising the steps of:

11. An X-ray scattering pattern acquisition means for acquiring an X-ray scattering pattern of a sample including a crystalline portion and an amorphous portion of a target substance; a pattern decomposition means for obtaining a diffraction pattern of the crystalline portion and a continuous pattern from the X-ray scattering pattern; a target substance intensity calculation means for calculating an integrated intensity relating to the target substance based on the X-ray scattering pattern and chemical formula information of the target substance; a target substance pattern calculation means for calculating a scattering pattern of the target substance including the crystalline portion and the amorphous portion from the continuous pattern such that the integrated intensity of the scattering pattern coincides with the integrated intensity calculated by the target substance intensity calculation means; a structural disorder parameter determining means for determining a structural disorder parameter of the crystalline portion based on a diffraction pattern of the crystalline portion and a scattering pattern of the target substance; and a crystallinity output means for outputting the crystallinity of the target substance calculated according to the determined structural irregularity parameter; A program that causes a computer to operate as a

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