Crystallinity measuring apparatus, crystallinity measuring 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 measuring apparatus, a crystallinity measuring method, and a program, and more particularly to the measurement of crystallinity using X-ray diffraction. [Background technology]

[0002] Polymers exist in two forms: crystalline and amorphous. However, even crystalline polymers are not entirely crystalline; they contain a mixture of crystalline and amorphous regions. The ratio of the weight of the crystalline region to the total weight of a crystalline polymer is called its crystallinity. Crystallinity is important information for understanding the properties of crystalline polymers, including their mechanical and chemical properties.

[0003] Among the various methods for measuring crystallinity, the method using X-ray diffraction has significant practical advantages, such as being independent of sample size in principle and being able to be performed non-destructively on the sample. [Overview of the project] [Problems that the invention aims to solve]

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

[0005] Therefore, in order to determine 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 in the crystalline portion of the target substance, its crystallinity is actually thought to be reduced. For this reason, the intensity of the diffraction pattern from the crystalline portion of the target substance is observed to be lower than it actually is, and as a result, the degree of crystallinity of the target substance is calculated to be lower than it actually is.

[0006] The present invention has been made in view of the above problems, and its purpose is to provide a crystallinity measuring device, a crystallinity measuring 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 problems, the crystallinity measuring apparatus according to 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 related to the target substance based on the X-ray scattering pattern and the chemical formula information of the target substance; a target substance pattern calculation means for calculating the 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 the 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 according to the determined structural irregularity parameter.

[0008] (2) In the crystallinity measuring apparatus described in (1), the structural irregularity parameter determination means includes a pseudocrystallinity calculation means that calculates a pseudocrystallinity for each of the plurality of structural irregularity factors, changing the given integration range, with the value 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 as the numerator, and the value obtained by integrating the scattering pattern of the target substance over the given integration range as the denominator; and a parameter selection means that calculates an evaluation value by substituting the plurality of pseudocrystallinity values ​​calculated for each of the plurality of structural irregularity parameters, changing the given integration range, into a predetermined evaluation formula, and selects one of the structural irregularity parameters based on the evaluation value.

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

[0010]

number

[0011] (4)(3) In the crystallinity measuring apparatus described above, the evaluation value may be given by the following equation S. Here, f n is the degree of pseudocrystallization relating to the nth integration range, and D0 is the fitting parameter.

[0012]

number

[0013] (5) In the crystallinity measuring apparatus described in any of (1) to (4), the sample may contain one or more crystalline fillers. The pattern decomposition means may obtain the diffraction patterns 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 the integral intensity of the diffraction pattern of one of the crystalline fillers. Alternatively, the integral intensity of the target substance may be calculated by multiplying the integral intensity of the one crystalline filler by a ratio corresponding to the chemical formula information of the crystalline filler and the target substance contained in the sample.

[0014] (6)(5) In the crystallinity measuring apparatus described above, the sample may contain one or more amorphous fillers.

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

[0016] (8)(7) In the crystallinity measuring apparatus described above, the background cormorant The subtraction means is the background cormorant A background intensity calculation means calculates the integrated intensity of the background based on the integrated intensity of the X-ray scattering pattern of the sample and the chemical formula information of the substance contained in the sample, and a background calculation means calculates the background such that its integrated intensity matches the integrated intensity calculated by the background intensity calculation means. cormorant It may include a means for calculating the value.

[0017] In the crystallinity measuring apparatus described in (9), (7), or (8), the target substance pattern calculation means is the background cormorant The scattering pattern of the target substance may be calculated by multiplying the continuous pattern obtained by subtracting the `nd` by a ratio corresponding to the integrated intensity calculated by the target substance intensity calculation means.

[0018] (10) The crystallinity measurement method according to the present invention includes: an X-ray scattering pattern acquisition step of acquiring an X-ray scattering pattern of a sample including the crystalline and amorphous portions of a target substance; a pattern decomposition step of acquiring a diffraction pattern and a continuous pattern of the crystalline portion from the X-ray scattering pattern; a target substance intensity calculation step of calculating the integrated intensity of the target substance based on the X-ray scattering pattern and the chemical formula information of the target substance; and the scattering pattern of the target substance including the crystalline and amorphous portions, and the integral intensity of the scattering pattern of the target substance including the crystalline and amorphous portions being used in the target substance intensity calculation step. Step The method includes: a target material pattern calculation step, which calculates a target material pattern from the continuous pattern so as to match the integrated intensity calculated by; a structural imperfection parameter determination step, which determines the structural imperfection parameter of the crystalline portion based on the diffraction pattern of the crystalline portion and the scattering pattern of the target material; and a crystallinity output step, which outputs the degree of crystallinity of the target material calculated according to the determined structural imperfection parameter.

[0019] (11) The program according to the present invention is a program for operating a computer, comprising: 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 related to the target substance based on the X-ray scattering pattern and the chemical formula information of the target substance; a target substance pattern calculation means for calculating the 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 the 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 according to the determined structural irregularity parameter. The program may be stored in a computer-readable information storage medium. [Brief explanation of the drawing]

[0020] [Figure 1] This is a configuration diagram of a crystallinity measuring apparatus according to an embodiment of the present invention. [Figure 2A] This figure schematically shows an example of the observation pattern of a sample. [Figure 2B] This diagram schematically shows the diffraction pattern of the crystalline portion of the target substance. [Figure 2C] This figure schematically shows an example of the diffraction pattern of a crystalline filler. [Figure 2D] This diagram schematically illustrates an example of a continuous pattern. [Figure 3A] This figure schematically shows an example of the X-ray scattering pattern of a sample when the entire target substance is amorphous. [Figure 3B] This figure schematically shows a reference continuum pattern created based on the X-ray scattering pattern shown in Figure 3A. [Figure 4] This is a functional block diagram of a crystallinity measuring device according to an embodiment of the present invention. [Modes for carrying out the invention]

[0021] One embodiment of the present invention will be described in detail below with reference to the drawings.

[0022] Figure 1 shows the configuration of a crystallinity measuring device according to one embodiment of the present invention. As shown in the figure, the crystallinity measuring device 10 includes an X-ray diffractometer 12, a calculation unit 14, a storage unit 16, and a display unit 18. However, when calculating the degree of crystallinity based on observation patterns obtained from another X-ray diffractometer, the crystallinity measuring device 10 does not need to include the X-ray diffractometer 12. In this case, the crystallinity measuring device 10 may consist of a calculation unit 14, a storage unit 16, and a display unit 18, and the storage unit 16 stores observation patterns obtained from other X-ray diffractometers in advance.

[0023] The X-ray diffractometer 12 performs X-ray diffraction measurements. Specifically, the X-ray diffractometer 12 incidents X-rays of a known wavelength onto the sample and measures the intensity of the scattered X-rays. The X-ray intensity data for each diffraction angle 2θ is output as an observation pattern from the X-ray diffractometer 12 to the calculation unit 14. The observation pattern output to the calculation unit 14 may be corrected by the Lorentz polarization factor (Lp correction). The X-ray diffractometer 12 uses a sufficiently small minimum angle 2θ of about 10 degrees. L Therefore, a sufficiently large maximum angle of about 120 degrees, 2θ H The intensity of scattered X-rays can be measured at each diffraction angle. In this specification, the X-ray intensity profile measured by the X-ray diffractometer 12 (data showing the change in X-ray intensity with respect to the change in diffraction angle) is referred to as the "X-ray scattering pattern" or "observation pattern". The X-ray scattering pattern is specifically called the "X-ray diffraction pattern" when the sample is crystalline.

[0024] In this embodiment, the sample to be measured for X-ray scattering patterns contains a target substance such as a powdery or fluid polymer, which may be partially crystalline and partially amorphous. One or more fillers are mixed into the sample. When preparing the sample, the type and weight of the substances constituting the sample are considered. fractionIt is known. The chemical formulas and chemical amounts of each substance are also known.

[0025] In the following, the sample is assumed to be in bulk solid form as an example. When such a sample is synthesized, a powdery or fluid polymer is mixed with several fillers. This mixture is then subjected to molding and heat treatment to produce the resin material for the product that is the sample. It should be noted that the present invention is applicable not only to bulk solid samples but also to powdered samples.

[0026] As such samples, the following high-performance engineering plastic As an example, we will consider the measurement of the crystallinity of a sample containing PPS (Polyphenyl Sulfide) resin, also known as PPS. This sample is assumed to contain calcium carbonate (CaCO3) as a crystalline filler and E-glass fibers as an amorphous filler. However, the present invention may be applied to the measurement of the crystallinity of various target substances in various samples other than the above sample. For example, crystalline and amorphous fillers do not need to be mixed in the sample. Alternatively, multiple types of crystalline fillers may be mixed in the sample. Similarly, multiple types of amorphous fillers may be mixed in the sample.

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

[0028] The display unit 18 is a display device that displays the calculation result by the arithmetic unit 14. For example, the display unit 18 displays the crystallinity of the target substance numerically or graphically.

[0029] Here, the procedure for calculating the crystallinity by the crystallinity measuring device 10 will be described. The calculation of the crystallinity is roughly divided into: (1) pattern decomposition, (2) calculation of the structural disorder parameter, (3) calculation of the integrated intensity of the pattern derived from each component, and (4) calculation of the pattern of the entire target substance (PPS).

[0030] (1) Pattern decomposition: When the observed pattern y(2θ), which is the X-ray scattering pattern of the sample, is obtained from the X-ray diffractometer 12, it is decomposed into a plurality of patterns. FIG. 2A schematically shows the observed pattern y(2θ). Total_obs As shown in the same figure, the observed pattern y(2θ) includes a number of peaks derived from one or more crystal components and a smooth continuous pattern. As described above, the sample contains the crystalline part and the amorphous part of PPS, the crystalline filler calcium carbonate, and the non-crystalline filler E-glass fiber. Therefore, as shown in the following formula (1), the observed pattern y(2θ) is decomposed into the diffraction pattern y(2θ) of the crystalline part of PPS, the diffraction pattern y(2θ) of the crystalline filler, and the continuous pattern y(2θ). Total_obs As shown in the figure, the observed pattern y(2θ) Total_obs includes a number of peaks derived from one or more crystal components and a smooth continuous pattern. As described above, the sample contains the crystalline part and the amorphous part of PPS, the crystalline filler calcium carbonate, and the non-crystalline filler E-glass fiber. Therefore, as shown in the following formula (1), the observed pattern y(2θ) Total_obs is decomposed into the diffraction pattern y(2θ) of the crystalline part of PPS, P_C the diffraction pattern y(2θ) of the crystalline filler, CF and the continuous pattern y(2θ). H

[0031]

Equation

[0032] FIG. 2B schematically shows the diffraction pattern y(2θ) of the crystalline part of PPS. P_C FIG. 2C schematically shows the diffraction pattern y(2θ) of the crystalline filler. CF FIG. 2D schematically shows the continuous pattern y(2θ). H

[0033] ​​In pattern decomposition, for example, whole-powder-pattern fitting (WPPF) methods such as the Rietveld method or whole-powder-pattern decomposition (WPPD) are used. In this case, pattern y(2θ) P_C and pattern y(2θ) CF These patterns are identified based on information about the lattice constants and other crystal structure parameters (structural parameters) of PPS and calcium carbonate.

[0034] Continuous pattern y(2θ) H For this, the known reference continuous pattern y(2θ) H 100 Based on this, the same pattern is identified. That is, the continuous pattern y(2θ) H We assume the following equation (2), where Sc is a variable parameter, which is a scale factor. 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]

number

[0036] By substituting equation (2) into equation (1), we obtain the observation pattern y(2θ) Total_obs This can be expressed as shown in equation (3).

[0037]

number

[0038] Reference continuous pattern y(2θ) H 100This was created based on the X-ray scattering pattern measured after the sample was thoroughly melted at a high temperature beforehand, completely amorphousizing the PPS. Figure 3A shows the X-ray scattering pattern of a sample in which the PPS has been completely amorphous in this manner. Since this pattern contains peaks due to crystalline fillers, removing these peaks yields the reference continuous pattern y(2θ) shown in Figure 3B. H 100 This can be obtained. Reference continuous pattern y(2θ) H 100 This includes continuous patterns caused by the amorphous portion of PPS, continuous patterns caused by amorphous fillers, and background cormorant It includes a continuous pattern y(2θ) H It is considered to be similar to the above. Therefore, in this embodiment, by fitting the scale factor Sc multiplied by the reference continuous pattern and the auxiliary function a(2θ), the continuous pattern y(2θ) is obtained. H I am trying to obtain it.

[0039] The pattern y(2θ) obtained as described above P_C and pattern y(2θ) CF This may be corrected by equations (4) and (5). Equations (4) and (5) are for the observed pattern y(2θ) Total_obs From this, a continuous pattern y(2θ) H The value obtained by subtracting this is y(2θ) P_C and y(2θ) CF By proportionally distributing the value of , y(2θ) CF obs and y(2θ) P_C obs This is to find the following values: y(2θ) P_C and y(2θ) CF Using this instead allows for a more accurate determination of the degree of crystallinity (DOC).

[0040]

number

[0041]

number

[0042] (2) Calculation of structural irregularity parameter: The degree of crystallinity DOC is expressed by the following equation (6). Here, w P_C PP S Weight of the crystal portion fraction And, w P_NC PP S Weight of the amorphous portion fraction That is the case.

[0043]

number

[0044] By the way, in the sample k When different types of substances are present, the integral intensity Y originates from the k-th substance. k and the weight of the same substance fraction w k The relationship between and is shown in equation (7). This relationship is also explained in, for example, J. Appl. Cryst. (2016). 49, 1508-1516, Japanese Patent Publication No. 6231726, and International Publication 2017 / 149913. Note that the integrated intensity Y k When calculating this, the integrand is obtained by multiplying the scattering pattern of the k-th substance by an Lp correction factor. The integration range is the entire range, for example, 2θ of about 10 degrees. L From approximately 120 degrees 2θ H That is the end.

[0045]

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

[0047]

number

[0048] According to equations (7) and (6), the degree of crystallinity DOC is expressed by the following equation (9). Here, Y P_C PP S This is the integral intensity of the crystalline portion, Y P_NC PP S This is the integral intensity of the amorphous portion, Y P PP S This is the overall integrated intensity.

[0049]

number

[0050] By the way, in materials like PPS, where crystalline and amorphous parts coexist, even the crystalline parts are thought to have reduced crystallinity. Therefore, y(2θ) P_C It is thought that this is observed to be lower than the actual value. Therefore, as shown in equation (10), the correction pattern y(2θ) P_C D Using PP S The integral intensity of the crystalline portion is calculated. Then, the corrected integral intensity calculated in this way is used as the numerator of equation (9) to obtain a more accurate degree of crystallinity. DOC We seek.

[0051]

number

[0052] Here, the correction pattern y(2θ) P_C D This is the original pattern y(2θ) P_CThis is obtained by multiplying by the structural irregularity factor shown in equation (11).

[0053]

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

[0055] That is, the integration range is 2θ L from 2θ n The partial integrated intensity of the crystalline portion of PPS is calculated using equation (12). The partial integrated intensity of the entire PPS is calculated using equation (13). Here, 2θ n θ is the diffraction angle that represents the upper limit of the integration range, and for example, it shows the nth angle when the range from approximately 60 degrees to approximately 120 degrees is divided into N sections. Also, G(2θ) is the Lp correction factor. "Partial integrated intensity" means the intensity obtained by integration over a part of the integration range. Note that among the integrands of equation (13), y(2θ) represents the scattering pattern of the entire PPS. P The method for calculating this will be explained later.

[0056]

number

[0057]

number

[0058] Then, using equations (12) and (13), the pseudocrystallization degree f is obtained as shown in equations (14) and (15). n Define.

[0059]

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[0060]

number

[0061] This pseudocrystallinity f n As the value of n increases, the value of k is thought to fluctuate above and below the true crystallinity value, eventually converging to the true crystallinity value. This is because large peaks that significantly affect the value of the integrated intensity exist intermittently in the low-angle region. Therefore, the value of the structural imperfection parameter k is considered likely when the evaluation value S shown in equation (16) is minimized. Here, D0 is a fitting (variable) parameter, and when fitting is complete, it approximates the true crystallinity value.

[0062]

number

[0063] In this embodiment, the value of the evaluation value S is calculated multiple times while changing the pair of structural imperfection parameter k and parameter D0, and the structural imperfection 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 imperfection parameter k is identified, k Using the value of 2θ, L from 2θ H The integration range is set to , and the true crystallinity DOC is determined by equation (14). Alternatively, the value of D0 above may be used as the true crystallinity DOC.

[0064] (3) Calculation of the integrated intensity of each component in the sample: Of the integrands in equation (13) above, y(2θ) represents the scattering pattern of the entire PPS. P To determine this, the integrated intensity of each component in the sample is calculated.

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

[0066]

number

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

[0068]

number

[0069] Next, by rearranging equation (7), we can obtain equation (19). This gives us the sum of the integral intensities Y of all substances contained in the sample. Total Y is the integral intensity of a single substance. CF This can be derived from equation (18).

[0070]

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[0071] Therefore, by substituting equations (17) and (19) into equation (20), we can obtain the integrated background intensity B P It is possible to find this.

[0072]

number

[0073] Furthermore, by rearranging equation (7), we can obtain equation (21). This gives us the integral intensity Y of the entire PPS. P Regarding this, Y is the integral intensity of a single substance. CF It can be derived from this.

[0074]

number

[0075] (4) Calculation of the scattering pattern y(2θ) of the entire PPS P : Here, the scattering pattern y(2θ) of the entire PPS P is derived from the continuous pattern y(2θ). As a prerequisite, the background pattern b(2θ) H is obtained. Here, the background pattern b(2θ) of the known alpha-SiO2 P is scaled by the following equation (22) to obtain the background pattern b(2θ) Si . P

[0076] [Number]

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

[0078] [Number]

[0079] Note that the background pattern b(2θ) of alpha-SiO2 Si was selected because the value of a calculated for the average chemical composition of the entire sample of this embodiment k is close to the value of a calculated for alpha-SiO2 k .

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

[0081] [Number]

[0082] This pattern y(2θ)​H_NC includes 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. Also, the scattering pattern y(2θ) of the entire PPS P is only used for calculation by integrating according to Equation (13). Therefore, according to the following Equation (24), the corrected continuous pattern y(2θ) H_NC is scaled to obtain the pattern y(2θ) of the entire PPS P to obtain.

[0083]

Number

[0084] Here, the integrated intensity Y H_NC can be calculated by the following Equation (26).

[0085]

Number

[0086] As described above, the scattering pattern y(2θ) of the entire PPS P can be obtained, and thereby the structural disorder parameter k can be calculated. Then, using the calculated k, a more accurate degree of crystallinity DOC can be obtained.

[0087] Here, we will describe the details of the crystallinity measurement device 10. Figure 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 strength calculation unit 103, a target substance pattern calculation unit 104, a structural irregularity parameter determination unit 105, and a crystallinity output unit 106. The pattern decomposition unit 102 includes a pattern recalculation unit 102a. The target substance strength calculation unit 103 includes a crystalline filler strength calculation unit 103a. The target substance pattern calculation unit 104 includes a background subtraction unit 104a, which in turn includes a background strength calculation unit 104b and a background calculation unit 104c. The structural irregularity parameter determination unit 105 includes a pseudo-crystallinity calculation unit 105a and a parameter selection unit 105b. These functions are realized by executing the crystallinity measurement program described above in the computer system, which is the arithmetic unit 14.

[0088] The observation pattern acquisition unit 101 obtains the observation pattern y(2θ), which is the X-ray scattering pattern of the sample, from the X-ray diffractometer 12. Total_obs Obtain it.

[0089] The pattern decomposition unit 102 uses the full pattern fitting method to determine the observed pattern y(2θ) Total_obs The diffraction pattern y(2θ) of the crystalline portion of PPS P_C And the pattern y(2θ) caused by crystalline fillers CF And, the continuous pattern y(2θ) H It is decomposed into and . In the pattern decomposition section 102, pattern y(2θ) P_C and pattern y(2θ) CF Regarding this, the patterns are identified based on the structural parameters of PPS and calcium carbonate. Furthermore, the continuous pattern y(2θ) is also identified. H For this, see the reference continuous pattern y(2θ) H 100 Based on this, identify the same pattern.

[0090] The pattern decomposition unit 102 includes a pattern recalculation unit 102a. The pattern recalculation unit 102a calculates y(2θ) according to equations (4) and (5). CF obs and y(2θ) P_C obs Observation pattern y(2θ) Total_obs We calculate from this. In the subsequent processing, we use y(2θ) obtained by pattern decomposition. CF and y(2θ) P_C Instead, y(2θ) CF obs and y(2θ) P_C obs This is used.

[0091] The target material strength calculation unit 103 calculates the integrated strength Y for the entire PPS (including the crystalline and amorphous portions). P The crystalline filler strength calculation unit 103a of the target material strength calculation unit 103 has an observation pattern y(2θ) Total_obs Diffraction pattern y(2θ) of crystalline filler obtained from CF This is given by the pattern decomposition unit 102. Then the crystalline filler intensity calculation unit 103a calculates the integral intensity Y of the diffraction pattern of the crystalline filler. CF This is calculated using equation (18). The target substance strength calculation unit 103 calculates the integral intensity Y of the diffraction pattern of the crystalline filler thus calculated. CF By multiplying this by a ratio corresponding to the crystalline fillers contained in the sample and the chemical formula information of the target substance, the integral intensity Y related to the target substance is obtained. P The integral intensity Y is calculated using equation (21). 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 portions). P The integral intensity is Y P The continuous pattern y(2θ) is made to match H It is calculated from this.

[0093] The background subtraction unit 104a of the target substance pattern calculation unit 104 calculates the continuous pattern y(2θ) corrected by equation (24). H_NC This is obtained. At this time, the background intensity calculation unit 104b calculates the background cormorant nd pattern b(2θ) P The integrated intensity BP is the integrated intensity y(2θ) of the X-ray scattering pattern of the sample. Total_obs The calculation is based on the chemical formula information of the substances contained in the sample (PPS, calcium carbonate, and E-glass fiber). Specifically, based on formulas (17) to (20), B P The background calculation unit 104c calculates the background pattern b(2θ) P The integral intensity is calculated such that it matches the integral intensity BP calculated by the background intensity calculation unit 104b. Specifically, the reference background is b(2θ) Si Using equation (22), the background pattern b(2θ) P Calculate.

[0094] The target material pattern calculation unit 104 calculates the corrected continuous pattern y(2θ) H_NC In contrast, the integrated intensity Y calculated by the target substance intensity calculation unit 103 P By multiplying by a ratio corresponding to the given value, the scattering pattern y(2θ) of the target substance can be obtained. P We calculate this. Specifically, using equation (25), y(2θ) P Calculate.

[0095] The structural irregularity parameter determination unit 105 determines the diffraction pattern y(2θ) of the crystalline portion of the PPS. P_C And the scattering pattern of the entire PPS, y(2θ) P Based on this, the structural irregularity parameter k of the crystalline portion of PPS is determined. The pseudocrystallinity calculation unit 105a calculates the pseudocrystallinity f according to equations (14) and (15). n Calculate.

[0096] The pseudocrystallinity calculation unit 105a calculates the pseudocrystallinity f by changing the values ​​of the structural irregularity parameter k and parameter D0 pair. n The evaluation value S shown in (1~N) and equation (16) is calculated. The parameter selection unit 105b selects a pair of values ​​for structural imperfection parameter k and parameter D0 that results in a small evaluation value S.

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

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

[0099] It should be noted that the present invention is not limited to the embodiments described above, and 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 of the target substance PPS P The integral intensity Y of the crystalline filler CF This was obtained from (Equation (21)). In addition, the integrated intensity B of the background P If is known, then the integral intensity Y of the observed pattern can be calculated using equation (20). Total_obs From the integrated intensity Y Total We find (equation (20)), and in the same manner as in equation (19), the integral intensity Y Total From the target substance PPS, the integrated intensity Y P In addition, the integrated intensity of all substances can be determined.

[0101] Furthermore, in the above embodiment, the corrected continuous pattern y(2θ) H_NC Scaling y(2θ) P This was done to obtain the following: In addition, the continuous pattern y(2θ) H_NCScaling the pattern y(2θ) of the amorphous portion of PPS P_NC Obtaining the pattern y(2θ) P_NC and y(2θ) P_C By adding this, y(2θ) P You may also obtain it.

Claims

1. X-ray scattering pattern acquisition means for acquiring the X-ray scattering pattern of a sample including the crystalline and amorphous portions of the target substance, A pattern decomposition means for obtaining the diffraction pattern and continuous pattern of the crystal portion from the aforementioned X-ray scattering pattern, A target substance intensity calculation means that calculates the integrated intensity related to the target substance based on the X-ray scattering pattern and the chemical formula information of the target substance, A target material pattern calculation means calculates a pattern used for integrating the scattering pattern of the target material including the crystalline portion and the amorphous portion from the continuous pattern such that the integrated intensity matches the integrated intensity calculated by the target material intensity calculation means, A structural imperfection parameter determination means for determining the structural imperfection parameter of the crystalline portion based on the integral value relating to the diffraction pattern of the crystalline portion and the integral value relating to the scattering pattern of the target material, Crystallinity output means for outputting the degree of crystallinity of the target substance calculated according to the determined structural irregularity parameter, A crystallinity measuring device that includes [specific components / features].

2. In the crystallinity measuring apparatus according to claim 1, The structural irregularity parameter determination means is A pseudocrystallinity calculation means calculates the pseudocrystallinity for each of the multiple structural irregularity factors, by changing the given integration range, with the value obtained by integrating a correction pattern, which is 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 as the numerator, and the value obtained by integrating the scattering pattern of the target substance over the given integration range as the denominator, A parameter selection means that calculates an evaluation value by substituting multiple pseudocrystallinity values, which are calculated for each of the multiple structural imperfection parameters while changing the given integration range, into a predetermined evaluation formula, and selects one of the structural imperfection parameters based on the evaluation value, A crystallinity measuring device, including a crystallinity measuring device.

3. In the crystallinity measuring apparatus according to claim 2, A crystallinity measuring device in which the structural imperfection factor is given by the following equation, where λ is the wavelength of the incident X-ray and k is the structural imperfection parameter. [Math 1]

4. In the crystallinity measuring apparatus according to claim 3, The aforementioned evaluation value is given by the following equation S, f n is the degree of pseudocrystallization relating to the nth integration range, and D 0 This is a fitting parameter for a crystallinity measuring device. [Math 2]

5. In the crystallinity measuring apparatus according to claim 1, The sample contains one or more crystalline fillers, The pattern decomposition means obtains the diffraction patterns of the one or more crystalline fillers from the X-ray scattering pattern. The aforementioned means for calculating the strength of the target substance is: The system includes a crystalline filler intensity calculation means for calculating the integral intensity of the diffraction pattern of the crystalline filler in 1, The integral intensity for the target substance is calculated by multiplying the integral intensity for the crystalline filler in 1 above by a ratio corresponding to the chemical formula information of the crystalline filler and the target substance contained in the sample. Crystallinity measuring device.

6. In the crystallinity measuring apparatus according to claim 5, The aforementioned sample contains one or more amorphous fillers, and is a crystallinity measuring device.

7. In the crystallinity measuring apparatus according to claim 1, The aforementioned continuous pattern includes background, The crystallinity measuring device includes a background subtraction means for subtracting the background from the continuous pattern, which is part of the target substance pattern calculation means.

8. In the crystallinity measuring apparatus according to claim 7, The background subtraction means is, A background intensity calculation means calculates the integrated background intensity based on the integrated intensity of the X-ray scattering pattern of the sample and the chemical formula information of the substance contained in the sample. A background calculation means that calculates the background such that its integrated intensity matches the integrated intensity calculated by the background intensity calculation means, A crystallinity measuring device, including a crystallinity measuring device.

9. In the crystallinity measuring apparatus according to claim 7 or 8, The crystallinity measuring device 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 is performed to acquire the X-ray scattering pattern of a sample including the crystalline and amorphous portions of the target substance, A pattern decomposition step to obtain the diffraction pattern and continuous pattern of the crystal portion from the X-ray scattering pattern, A target substance intensity calculation step, which calculates the integrated intensity related to the target substance based on the X-ray scattering pattern and the chemical formula information of the target substance, A target material pattern calculation step is performed in which a pattern used for integrating the scattering pattern of the target material including the crystalline portion and the amorphous portion is calculated from the continuous pattern such that its integrated intensity matches the integrated intensity calculated in the target material intensity calculation step, A structural imperfection parameter determination step in which the structural imperfection parameter of the crystalline portion is determined based on the integral value relating to the diffraction pattern of the crystalline portion and the integral value relating to the scattering pattern of the target material, A crystallinity output step that outputs the crystallinity of the target substance calculated according to the determined structural irregularity parameter, A method for measuring crystallinity, including [specific component].

11. X-ray scattering pattern acquisition means for acquiring the X-ray scattering pattern of a sample including the crystalline and amorphous portions of a target substance. Pattern decomposition means for obtaining the diffraction pattern and continuous pattern of the crystal portion from the X-ray scattering pattern, A target substance intensity calculation means that calculates the integrated intensity related to the target substance based on the X-ray scattering pattern and the chemical formula information of the target substance. A target material pattern calculation means calculates a pattern used for integrating the scattering pattern of the target material including the crystalline portion and the amorphous portion from the continuous pattern such that the integrated intensity matches the integrated intensity calculated by the target material intensity calculation means. A structural imperfection parameter determination means for determining the structural imperfection parameter of the crystal portion based on the integral value relating to the diffraction pattern of the crystal portion and the integral value relating to the scattering pattern of the target material, and Crystallinity output means for outputting the degree of crystallinity of the target substance calculated according to the determined structural imperfection parameter. A program used to operate a computer.

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