X-ray diffraction method for polymer characterization

Abstract

The present invention provides an analytical device and an analytical method that can measure the movement of polymers on a surface (interface) and obtain information about the vicinity of the surface of an object to be observed without labeling by observing the polymers in a state of total reflection of X-rays. [Solution] An analytical device that can irradiate a polymer with X-rays at angles around the total reflection angle of the polymer and obtain time-resolved diffraction and scattering images; and a method for analyzing polymers, which includes the steps of irradiating a polymer sample with X-rays at the total reflection angle of the X-rays, obtaining time-resolved diffraction and scattering images, and evaluating the mobility of the polymer surface.

Description

Technical Field

[0001] The present disclosure relates to a polymer measurement apparatus and a measurement method using X-ray diffraction.

Background Art

[0002] Various measurement apparatuses and measurement methods using X-ray diffraction are known. Patent Document 1 discloses a motion measurement apparatus that can evaluate the motion of an object by attaching a label to the observation target and using a simple X-ray source that can reduce damage.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In Patent Document 1, a label (for example, a gold nanocrystal) for the observation target is essential, and only averaged bulk information can be obtained for the observation target.

Means for Solving the Problems

[0005] The present disclosure provides an analyzer that can irradiate a polymer with X-rays at an incident angle around the critical angle (the maximum angle at which X-rays are totally reflected) and acquire a time-division diffraction / scattering image. In addition, the present disclosure provides an analyzer including an X-ray source unit that irradiates X-rays, a sample stage unit on which a sample is placed, a detection unit that detects X-rays from the sample, and a signal processing unit that processes a signal detected by the detection unit. The analyzer is preferably provided with: a beam irradiation unit that irradiates a polymer with X-rays at an incident angle around the critical angle, a sensor unit that detects diffracted / scattered X-rays from the sample, a signal extraction unit that extracts a signal in a detection window set in the sensor unit and is preferably provided with. Furthermore, this disclosure describes a process of irradiating a polymer sample with X-rays at an incident angle around the critical angle. A process for detecting diffracted and scattered X-rays from a sample, and Process for acquiring time-resolved diffraction and scattering images The present invention provides a method for analyzing polymers, which has the following properties: Various polymers can be evaluated using the analytical apparatus and analytical method described herein.

[0006] According to this disclosure, the motion of polymers at a surface (interface) can be measured. By observing the polymer while controlling the temperature under conditions of total internal reflection of X-rays, motion information near the surface of the observed object can be obtained without labeling. Furthermore, by performing measurements in a low-temperature environment, the motion when water or ice is present on the polymer surface can also be measured.

[0007] Preferred embodiments of this disclosure are as follows: Appearance 1: This analytical device irradiates polymers with X-rays at incident angles close to the critical angle for X-rays, and can acquire time-resolved diffraction and scattering images. Appearance 2: The analytical apparatus according to Embodiment 1, which can obtain time-resolved diffraction and scattering images of a polymer sample even when a substance that transmits X-rays is present on the surface of the polymer sample. Appearance 3: The analytical apparatus according to embodiment 1 or 2, which can obtain a scattering and diffraction pattern of an X-ray-transmitting substance when the substance is present on the surface of a polymer sample. Appearance 4: The analytical device, A beam irradiation unit that irradiates polymers with X-rays at incident angles around the critical angle. Sensor unit for detecting X-rays from the sample, Signal extraction unit that extracts signals from the detection window set in the sensor unit. An analytical apparatus according to any one of embodiments 1 to 3, comprising the above. Appearance 5: The analytical apparatus according to embodiment 4, which has a mechanism for causing total internal reflection of X-rays by controlling the movement of at least one of the X-ray source unit that irradiates with X-rays and the sample stage unit on which the sample is placed, and which can set the incident angle of the X-rays incident on the sample to a minute angle with respect to the surface. Appearance 6: A process of irradiating a polymer sample with X-rays at an incident angle around the critical angle. A process for detecting X-rays from a sample, and a process for obtaining time-resolved diffraction and scattering images to evaluate the mobility of the polymer surface. A method for analyzing polymers, comprising [the specified characteristic]. Appearance 7: The analytical method according to embodiment 6, wherein the incident angle of the X-rays in the step of irradiating the polymer sample is 0.001° to 5°. Aspect 8: The analytical method according to embodiment 6 or 7, wherein the step of detecting X-rays from a sample is performed using an HPAD (Hybrid Pixel Array Detector) whose distance from the sample can be arbitrarily adjusted. Appearance 9: The analytical method according to any one of embodiments 6 to 8, wherein the set temperature of the temperature control device is -100°C to 300°C in the step of acquiring time-resolved diffraction and scattering images. Appearance 10: An analytical method according to any of embodiments 6 to 9, wherein the step of evaluating the mobility of a polymer surface uses the DXT method (Diffracted X-ray Tracking) or the DXB method (Diffracted X-ray Blinking), and further uses the ACF (Autocorrelation Function). [Effects of the Invention]

[0008] According to this disclosure, time-resolved measurements specifically for the vicinity of a polymer surface can be performed without requiring labeling (e.g., gold nanocrystals) on the object being observed. In this disclosure, the objects of observation are polymers, particularly synthetic polymers. The introduction of total internal reflection measurement allows for highly sensitive measurement of molecular-level motion near the surface (interface). [Brief explanation of the drawing]

[0009] [Figure 1] The 2D (two-dimensional) GI-WAXD (Grazing Incidence Wide Angle X-ray Diffraction) diffraction profile with a time resolution of 500 milliseconds at 20 °C for the polymer of Synthesis Example 1. [Figure 2] The 2D GI-WAXD diffraction profile with a time resolution of 500 milliseconds at -15 °C for the polymer of Synthesis Example 1 in a state where condensed water is present on the sample surface. [Figure 3] Autocorrelation functions and attenuation coefficient distribution diagrams obtained in Examples Ⅰ to Ⅳ. [Figure 4] Attenuation coefficient distribution diagrams obtained in Examples Ⅴ to Ⅹ. [Figure 5] Autocorrelation functions and attenuation coefficient distribution diagrams obtained in Comparative Examples Ⅰ and Ⅱ.

Mode for Carrying Out the Invention

[0010] According to the present disclosure, X-rays can be irradiated onto a polymer at an incident angle around the critical angle, and a time-divided diffraction / scattering image can be obtained without labeling the object to be observed. According to the present disclosure, a total reflection diffraction system can be introduced to highly sensitively measure the molecular dynamics near the polymer surface.

[0011] In the present disclosure, the molecular dynamics can be measured by the DXT method (Diffracted X-ray Tracking; X-ray single molecule tracking method). The DXT method is a technique for evaluating molecular dynamics from the intensity and position of transmitted-type white X-ray diffraction points (Laue spots) from labeled crystals, and is a method capable of measuring molecular dynamics with high resolution both in space and time. Spatial division observation with a maximum of picometers in translational motion conversion is possible, and measurement is possible with a time resolution of microseconds to milliseconds. The highest measurement speed reported to date is time-divided observation of several hundred nanoseconds. So far, molecular dynamics measurement has been realized in various systems and is used for measuring intramolecular motions of many molecules such as DNA and membrane protein molecules.

[0012] In this disclosure, the use of the DXB method (Diffracted X-ray Blinking) is preferred. The DXB method is a technique that uses monochromatic X-rays to evaluate molecular dynamics from changes in the intensity of Laue spots. Dynamic information is discussed by analyzing the fluctuations (blinking) of diffraction spots = diffraction intensity that enter and exit the Debye-Scherraer ring, which is the observation range. This method makes the time resolution of the DXT method, which was previously only possible with high-intensity devices using white X-rays such as large synchrotron radiation facilities, possible even with general-purpose X-ray diffractometers. The application of the DXB method to polymers was previously unknown. The DXB method is a technique that uses diffracted X-rays to evaluate molecular dynamics and can measure with a time resolution of several milliseconds to several seconds. Because the DXB method uses monochromatic X-rays, it is highly versatile and causes less damage to the object being measured compared to white X-rays, so long-term measurements on the order of milliseconds to seconds are possible. The DXB method is a technique that can be measured even with a general-purpose X-ray diffractometer at the laboratory level, and it is a simple and quick method for performing polar time-resolved X-ray diffraction measurements.

[0013] In this disclosure, it is preferable to use GIXD (Grazing Incidence X-ray Diffraction). In GIXD, total internal reflection occurs when X-rays are incident on a sample at an angle smaller than the critical angle, just above the surface of the sample (i.e., at a small angle of incidence). This is because the refractive index of the material with respect to X-rays is slightly less than 1. By incidenting X-rays at angles of incidence around the critical angle and measuring the scattering and diffraction of the X-rays, the aggregation state near the outermost surface and inside the sample can be discussed.

[0014] In this disclosure, it is preferable to use an ACF (Autocorrelation Function). Two-dimensional X-ray diffraction images are taken with a time resolution of several milliseconds to several seconds, capturing 100 to 10,000 images, for example, about 2,000 images. For each pixel, the time-series change in diffraction intensity is extracted, and analysis is performed using the autocorrelation function. In equation TIFF2023075325000002.tif952, y0 is the convergence value of the autocorrelation function, A is the damping range, and T is the damping coefficient, i.e., the damping rate of the autocorrelation function. The larger the value of the damping coefficient T, the faster the damping (i.e., the higher the kinetic energy).

[0015] According to this disclosure, by controlling the temperature during measurement, it is possible to capture the mobility of molecular chains on the surface of a polymer thin film, the motion behavior of water / ice on the polymer thin film, and the movement of molecular chains on the polymer surface at the water / ice interface.

[0016] The X-ray analyzer described herein incorporates a mechanism into an X-ray diffractometer that causes total internal reflection of X-rays incident on a sample at the sample surface. The X-ray diffractometer may be a general-purpose X-ray diffractometer.

[0017] The X-ray diffractometer preferably comprises an X-ray source unit for irradiating with X-rays, a sample stage unit for placing the sample, a detection unit for detecting X-rays from the sample, and a signal processing unit for processing the signals detected by the detection unit. Either the X-ray source unit or the sample stage unit, or both, incorporate a mechanism to cause total internal reflection of the X-rays incident on the sample surface.

[0018] The X-ray diffraction apparatus may be, for example, the motion measurement apparatus described in Japanese Patent Publication No. 2018-84447. The disclosure of this publication is incorporated into this specification by reference. This motion measurement apparatus comprises a beam irradiation unit that irradiates a sample with a quantum beam (X-rays), a sensor (sensor unit) that detects the quantum beam from the sample, and a signal extraction unit that extracts a signal in a predetermined detection window set in the sensor. In this motion measurement apparatus, labeling is used, but in this disclosure, since a crystalline synthetic polymer is used as the object of measurement, labeling is generally unnecessary.

[0019] The beam irradiation unit irradiates with X-rays as a quantum beam. The sensor unit has a sensor that detects diffracted X-rays. The signal extraction unit gradually extracts the detection intensity measured by multiple pixels (detection windows) arranged within the detection area of ​​the sensor's detection surface as data.

[0020] A mechanism for causing total internal reflection of X-rays can, for example, set the incident angle of the X-rays incident on the sample to a minute relative to the surface (for example, 5° or less, 1° or less, or 0.1° or less, for example, 0.05°). In the motion measurement device described in Japanese Patent Application Publication No. 2018-84447, a control device controls the operation of the sample stage via a stage drive unit, and can adjust the position and orientation of the sample cell supported by the sample stage, thereby adjusting the incident angle of the X-rays incident on the sample.

[0021] The maximum angle at which X-rays undergo total internal reflection (critical angle) varies depending on the type of polymer. Generally, the angle of incidence on the polymer at which total internal reflection occurs (the angle between the direction of incidence and the polymer surface when X-rays are incident) can be between 0.001° and 5°, for example, between 0.01° and 4° or between 0.03° and 3°. Alternatively, the angle of incidence can be between 0.01° and 3°, or between 0.02° and 2° or between 0.03° and 1.5°.

[0022] X-rays may be white or monochromatic, but monochromatic is preferable from the viewpoint of reducing damage to the sample. When monochromatic X-rays are used, changes in X-ray intensity are detected as clear flashing (blinking X-ray). The wavelength of the X-rays is generally 0.01 Å to 100 Å, for example, 0.1 Å to 10 Å, and especially 0.5 Å to 5 Å.

[0023] The motion characteristics of diffraction spots can be evaluated by measuring the autocorrelation function of X-ray diffraction intensity and determining the attenuation coefficient. Diffraction spots can be represented as, for example, sharp patterns or halo (continuous) patterns, depending on their intensity and size. The motion characteristics of diffraction spots can be quantified using the autocorrelation function and the attenuation coefficient distribution.

[0024] Methods for analyzing polymers are: A process of irradiating a polymer sample with X-rays at an incident angle around the critical angle. A step of detecting X-rays from a sample, and A process for acquiring time-resolved diffraction and scattering images and evaluating the mobility of the polymer surface. It holds.

[0025] In the process of irradiating a polymer sample, the incident angle of the X-rays may be 0.001° to 5°, for example, 0.01° to 4° or 0.03° to 3°. The incident angle of the X-rays is the incident angle around the critical angle, and is the angle at which the X-rays penetrate the sample (on the order of μm or larger, for example, 1 μm or larger or 10 μm or larger) or pass through the sample, near the angle at which the X-rays undergo total internal reflection and the angle at which the X-rays undergo the maximum angle of total internal reflection (critical angle). The incident angle of the X-rays is not limited, but the lower limit may be 0.001°, 0.005°, 0.01°, 0.03°, 0.05°, 0.07°, 0.1°, 0.15°, 0.2°, 0.3°, 0.4°, 0.5°, 0.6°, 0.7°, or 0.8°, and the upper limit may be 5°, 4°, 3.5°, 3°, 2.5°, 2°, 1.5°, 1.2°, or 1°.

[0026] In the process of detecting X-rays that have been totally reflected, diffracted, and scattered from a sample, the detector may be a commonly used detector. As a two-dimensional detection unit, a Hybrid Pixel Array (HPAD), which is used in synchrotron radiation facilities worldwide, is preferred from the viewpoint of having a high readout speed, enabling shutterless measurement, and having low noise. Furthermore, the distance between the sample and the HPAD is preferably adjustable arbitrarily according to the molecular dynamics of the structure to be acquired, from the viewpoint of acquiring molecular dynamics information regarding structures of the order of Å to μm in the sample.

[0027] Next, the motion of all X-ray diffraction spots from the sample is tracked in time-resolved order to obtain time-resolved diffraction and scattering images, and the mobility of the polymer surface is evaluated. Time-resolved measurements of several milliseconds are possible. Two-dimensional X-ray diffraction images can be taken at a time resolution of several milliseconds to several seconds, with 100 to 10,000 images, for example, about 2,000 images. By calculating the ACF (Autocorrelation Function) of the X-ray diffraction intensity and determining the attenuation coefficient, the motion characteristics of the diffraction spots can be easily evaluated.

[0028] Specific examples of this disclosure are described below.

[0029] Rf group-containing polymer: [ka] The following analysis was performed. The fluoroalkyl group (hereinafter referred to as Rf group)-containing polymer is the same as the synthetic polymer produced in Example (Synthesis Example 1). A 1% solution of the synthetic polymer was spin-coated onto a silicon substrate at 2000 rpm for 30 seconds. Two samples of this polymer-coated substrate were prepared: one that was heat-treated at 100°C for 10 minutes, and another that was not heat-treated. Measurements were performed on both samples. Monochromatic X-rays (wavelength 1.5418 Å (CuKα)) were used. The heat-treated polymer sample showed a sharp pattern (considered to be crystalline), while the unheat-treated polymer sample showed a halo (continuous) pattern (amorphous compared to the former).

[0030] (1) 2D GI-WAXD diffraction profile For the polymer from Synthesis Example 1, a 2D GI-WAXD diffraction profile was obtained at 20°C with a time resolution of 500 milliseconds. The diffraction profile is shown in Figure 1. Figure 1 shows that diffraction profiles can be obtained regardless of whether heat treatment is performed, and that there are differences in the two-dimensional aggregation structure of Rf groups and the orientation of their higher-order structures with and without heat treatment.

[0031] (2) Diffraction profile when condensed water is present on the sample surface For the polymer from Synthesis Example 1, a 2D GI-WAXD diffraction profile was obtained at a time resolution of 500 milliseconds under -15°C conditions with condensed water present on the sample surface. The diffraction profile is shown in Figure 2. We observed condensate halos and profiles that appear to represent ice crystals. This suggests that the behavior of condensed water may differ depending on the aggregation state of the Rf groups. In the case without heat treatment, the water halo disappeared and diffraction, which is thought to be ice crystal, was observed, while in the case with heat treatment, only the water halo was observed. This suggests that the molecular chain aggregation structure influences the release of supercooling, and that a regular aggregation structure may delay the release of supercooling. [Examples]

[0032] The present disclosure will be specifically described below with reference to examples and comparative examples, but this description is not intended to limit the present disclosure.

[0033] X-ray diffraction measurements were performed using the following equipment and conditions. (1) Examples 1-4 X-ray machine: Rigaku MicroMax-007HF Detector: Rigaku PILATUS (pixel apparatus for the SLS) 3R 200K-A X-ray wavelength: 1.5418 Å (CuKα) Beam angle: 0.05° Temperature controller: Japan High-Tech Co., Ltd. Peltier-type cooling and heating stage 10021 for microscopes Detection distance: 50mm Exposure time: 50 milliseconds Number of shots: 2000 frames

[0034] (2) Examples 5-6 X-ray machine: Rigaku MicroMax-007HF Detector: Rigaku PILATUS (pixel apparatus for the SLS) 3R 200K-A X-ray wavelength: 1.5418 Å (CuKα) Beam angle: 0.07° Temperature controller: Japan High-Tech Co., Ltd. Peltier-type cooling and heating stage 10021 for microscopes Detection distance: 55mm Exposure time: 50 milliseconds (Example 5), 500 milliseconds (Example 6) Number of shots: 2000 frames

[0035] (3) Examples 7-8 X-ray machine: Rigaku MicroMax-007HF Detector: Rigaku PILATUS (pixel apparatus for the SLS) 3R 200K-A X-ray wavelength: 1.5418 Å (CuKα) Beam angle: 0.22° Temperature controller: Japan High-Tech Co., Ltd. Peltier-type cooling and heating stage 10021 for microscopes Detection distance: 55mm Exposure time: 50 milliseconds (Example 7), 500 milliseconds (Example 8) Number of shots: 2000 frames

[0036] (4) Examples 9-10 X-ray machine: Rigaku MicroMax-007HF Detector: Rigaku PILATUS (pixel apparatus for the SLS) 3R 200K-A X-ray wavelength: 1.5418 Å (CuKα) Beam angle: 1.0° Temperature controller: Japan High-Tech Co., Ltd. Peltier-type cooling and heating stage 10021 for microscopes Detection distance: 55mm Exposure time: 50 milliseconds (Example 9), 500 milliseconds (Example 10) Number of shots: 2000 frames

[0037] (5) Comparative Examples 1-2 X-ray machine: Rigaku MicroMax-007HF Detector: Rigaku PILATUS (pixel apparatus for the SLS) 3R 200K-A X-ray wavelength: 1.5418 Å (CuKα) Irradiation angle: Transmission (90°) Temperature controller: Japan High-Tech Co., Ltd. Peltier-type cooling and heating stage for microscopes 10084L Detection distance: 70mm Exposure time: 50 milliseconds Number of shots: 2000 frames

[0038] Synthesis Example 1 10.1 g of 1H,1H,2H,2H-Heptadecafluorodecyl Acrylate (a commercially available reagent from Tokyo Chemical Industry Co., Ltd.) was placed in a reaction vessel, the reaction flask was purged with nitrogen, and then 0.04 g of 2,2-azobisisobutyronitrile was added. The mixture was reacted overnight at 65°C to obtain 8.8 g of polymer (hereinafter referred to as compound A). The weight-average molecular weight of compound A was approximately 570,000 (PMMA equivalent).

[0039] Example 1 A 1% solution of compound A obtained in Synthesis Example 1 was spin-coated onto a silicon substrate at 2000 rpm for 30 seconds, and then annealed at 100°C for 10 minutes. This substrate was placed on a temperature-controlled device, and measurements were performed at 10°C. The motion characteristics of the diffraction spots were evaluated by measuring the autocorrelation function of the X-ray diffraction intensity and determining the attenuation coefficient. The autocorrelation function and attenuation coefficient distribution diagram at this time are shown in Figure 3 (top figure).

[0040] Example 2 A 1% solution of compound A obtained in Synthesis Example 1 was spin-coated onto a silicon substrate at 2000 rpm for 30 seconds, and then annealed at 100°C for 10 minutes. This substrate was placed on a temperature-controlled device, and measurements were performed at -10°C. The motion characteristics of the diffraction spots were evaluated by measuring the autocorrelation function of the X-ray diffraction intensity and determining the attenuation coefficient. The autocorrelation function and attenuation coefficient distribution diagram at this time are shown in Figure 3 (top figure).

[0041] Example 3 A 1% solution of compound A obtained in Synthesis Example 1 was spin-coated onto a silicon substrate at 2000 rpm for 30 seconds. This substrate was placed on a temperature-controlled device and measurements were performed at 10°C. The motion characteristics of the diffraction spots were evaluated by measuring the autocorrelation function of the X-ray diffraction intensity and determining the attenuation coefficient. The autocorrelation function and attenuation coefficient distribution diagram at this time are shown in Figure 3 (below).

[0042] Example 4 A 1% solution of compound A obtained in Synthesis Example 1 was spin-coated onto a silicon substrate at 2000 rpm for 30 seconds. This substrate was placed on a temperature-controlled device and measurements were performed at -10°C. The motion characteristics of the diffraction spots were evaluated by measuring the autocorrelation function of the X-ray diffraction intensity and determining the attenuation coefficient. The autocorrelation function and attenuation coefficient distribution diagram at this time are shown in Figure 3 (below).

[0043] Examples 5-10 A 1% solution of compound A obtained in Synthesis Example 1 was spin-coated onto a silicon substrate at 2000 rpm for 30 seconds, and then annealed at 100°C for 10 minutes. This substrate was placed on a temperature-controlled device, and measurements were performed at 20°C. The motion characteristics of the diffraction spots were evaluated by measuring the autocorrelation function of the X-ray diffraction intensity and determining the attenuation coefficient. The attenuation coefficient distribution at this time is shown in Figure 4.

[0044] Comparative Example 1 0.05 g of compound A obtained in Synthesis Example 1 was placed on polyimide paper (Kapton® paper), heated to 130°C to melt, then sandwiched between another sheet of Kapton paper, and transmission measurements were performed at 10°C. The motion characteristics of the diffraction spots were evaluated by measuring the autocorrelation function of the X-ray diffraction intensity and determining the attenuation coefficient. The autocorrelation function and attenuation coefficient distribution diagram at this time are shown in Figure 5.

[0045] Comparative Example 2 0.05 g of compound A obtained in Synthesis Example 1 was placed on polyimide paper (Kapton® paper), heated to 130°C to melt, then sandwiched between another sheet of Kapton paper, and transmission measurements were performed at -10°C. The motion characteristics of the diffraction spots were evaluated by measuring the autocorrelation function of the X-ray diffraction intensity and determining the attenuation coefficient. The autocorrelation function and attenuation coefficient distribution diagram at this time are shown in Figure 5.

[0046] Similar to Comparative Examples 1 and 2, in Examples 1 to 10, the motion characteristics of diffraction spots could be evaluated by determining the attenuation function from the change in X-ray diffraction intensity. Table 1 shows the results for Examples 1-10 and Comparative Examples 1 and 2.

[0047] [Table 1] [Industrial applicability]

[0048] According to the analytical apparatus and analytical method of this disclosure, time-resolved measurements specifically for the vicinity of the polymer surface can be performed without requiring labeling (e.g., gold nanocrystals) on the object being observed. The analytical apparatus and analytical method described herein can easily and quickly determine the molecular mobility near the surface of a polymer, and are considered effective for analyzing the surface properties of polymers.

[0049] Additional preferred embodiments of this disclosure are as follows: Appearance 1: This analytical device irradiates polymers with X-rays at incident angles close to the critical angle for X-rays, and can acquire time-resolved diffraction and scattering images. Appearance 2: The analytical apparatus according to Embodiment 1, which can obtain time-resolved diffraction and scattering images of a polymer sample even when a substance that transmits X-rays is present on the surface of the polymer sample. Appearance 3: The analytical apparatus according to embodiment 1 or 2, which can obtain a scattering and diffraction pattern of an X-ray-transmitting substance when the substance is present on the surface of a polymer sample. Appearance 4: A process of irradiating a polymer sample with X-rays at an incident angle around the critical angle. A process for acquiring time-resolved diffraction and scattering images and evaluating the mobility of the polymer surface. A method for analyzing polymers, comprising [the specified characteristic]. Appearance 5: The analytical method according to embodiment 4, wherein the incident angle of the X-rays in the step of irradiating the polymer sample is 0.001° to 5°. Appearance 6: The analytical method according to embodiment 4 or 5, wherein the step of detecting X-rays from a sample is performed by detection using an HPAD (Hybrid Pixel Array Detector). Appearance 7: An analytical method according to any of embodiments 4 to 6, wherein the step of evaluating the mobility of a polymer surface uses the DXT method (Diffracted X-ray Tracking) or the DXB method (Diffracted X-ray Blinking), and further uses the ACF (Autocorrelation Function).

Claims

1. An analytical device that can irradiate a polymer and water and / or ice on the surface of the polymer with X-rays at an incident angle near the critical angle and obtain time-resolved diffraction / scattering images.

2. 2. The analytical device according to claim 1, wherein a time-resolved diffraction / scattering image of a polymer sample can be obtained even if a substance through which X-rays transmit is present on the surface of the polymer sample.

3. 2. The analytical device according to claim 1, wherein, when a material through which X-rays transmit is present on the surface of a polymer sample, a scattering / diffraction image of the material through which X-rays transmit can be obtained.

4. The analytical device a beam irradiation unit that irradiates the polymer with X-rays at an incident angle around the critical angle; A sensor unit that detects X-rays from the sample; A signal extraction section that extracts the signal from the detection window set in the sensor section The analysis device according to any one of claims 1 to 3, comprising:

5. 5. The analytical instrument according to claim 4, further comprising a mechanism for totally reflecting X-rays by controlling the movement of at least one of an X-ray source unit that irradiates X-rays and a sample stage unit on which a sample is placed, and capable of setting the angle of incidence of the X-rays incident on the sample to a very small angle with respect to the surface.

6. A step of irradiating a polymer sample and water and / or ice on the surface of the polymer sample with X-rays at an incident angle around the critical angle; detecting X-rays from the polymer sample and the water and / or ice on the surface of the polymer sample; and acquiring a time-resolved diffraction / scattering image and evaluating the mobility of the polymer surface and the water and / or ice; A method for analyzing a polymer surface and water and / or ice present on the surface of the polymer, comprising:

7. 7. The method according to claim 6, wherein in the step of irradiating the polymer sample with X-rays, the angle of incidence of the X-rays is 0.001° to 5°.

8. 7. The analytical method according to claim 6, wherein in the step of detecting X-rays from the sample, the detection is performed by an HPAD (hybrid pixel array detector).

9. 7. The analytical method according to claim 6, wherein in the step of acquiring a time-resolved diffraction / scattering image, the temperature control device is set at a temperature of -100°C to 300°C.

10. The analytical method according to any one of claims 6 to 9, wherein in the step of evaluating the mobility of the polymer surface, a DXT method (Diffracted X-ray Tracking; X-ray single molecule tracking method) or a DXB method (Diffracted X-ray Blinking; X-ray diffraction blinking observation) is used, and an ACF (Autocorrelation Function) is further used.

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