JP6572726B2 - Sample measuring apparatus and sample measuring method - Google Patents

Description

  The present invention relates to a sample measurement device and a sample measurement method, and more specifically to a sample measurement device and a sample measurement method for measuring the molecular orientation or crystallinity of a sample.

  Conventionally, an X-ray analysis method, an ultrasonic method, a mechanical breaking strength method, and a birefringence method are known as methods for obtaining the molecular orientation of a sheet-like sample. However, the X-ray analysis method has a problem that the apparatus is large, the measurement takes time and labor, and only the molecular orientation of the crystal portion can be analyzed. In addition, the ultrasonic method requires a relatively large sample, is easily affected by the contact state and contained moisture, and has a problem that measurement is difficult when the sample is a thin sheet. In addition, the mechanical breaking strength method takes time for sampling and measurement, and has a problem that a measured sample cannot be used for another measurement because it is a fracture measurement. Further, the birefringence method has a problem that it cannot be measured when the sample is colored or when the sample is opaque.

  In contrast to these methods, the microwave method is a method for measuring the molecular orientation of a sheet-like sample from the dielectric anisotropy, and the sheet-like sample is inserted into a slit provided in a rectangular microwave cavity resonator. This is a method for obtaining molecular orientation by plotting the transmitted microwave intensity during one rotation of the sample in polar coordinates (for example, Patent Document 1). The microwave method is used as a means for measuring the molecular orientation of a biaxially stretched film. However, a rotating mechanism such as a motor is necessary to rotate the sample, and the structure of the measuring apparatus becomes complicated. is there.

  On the other hand, various methods have been devised for measuring the crystallinity of the polymer film, and X-ray analysis method, DSC (differential scanning calorimetry) method and There is a density method. The X-ray analysis method is a method that utilizes the fact that the diffracted X-rays have the same phase due to the relationship between the distance between crystal lattices and the Bragg angle, and strengthen each other. There is a problem that the measurement takes a lot of time and labor. The DSC method is a method for calculating the degree of crystallinity from the ratio of the heat of fusion of a sample to the heat of fusion of a complete crystal. However, like the X-ray analysis method, there is a problem that much time and labor are required for measurement. is there.

  The density method is a method of calculating the degree of crystallinity from the known crystal and amorphous densities and the measured sample density. In the density method, a density gradient tube is generally used. A density gradient tube uses a liquid with a high specific gravity and a light liquid to change the density continuously in an elongated glass tube. In the density method, a sample piece is put from above the density gradient tube, The density of the sample is measured by reading the scale (density) at the position where the density balances after settling and stops. However, it takes about one hour for the sample piece to settle and stop completely, and when there are many types of samples, it is difficult to identify the sample piece, especially in the case of a transparent film, etc. The problem is that it takes time and effort.

  In contrast to these methods, a method of measuring the crystallinity using a calibration curve from the dielectric loss rate has been devised as an application of the microwave method, which is one of the methods for obtaining the molecular orientation described above. In order to measure the crystallinity with more accuracy and canceling the directionality, it is necessary to provide a rotation mechanism such as a motor for rotating the sample, which causes a problem that the mechanism becomes complicated and expensive (Patent Literature). 2).

  On the other hand, as a method for measuring a trace amount of water contained in a sheet-like sample, a method using a rectangular microwave cavity resonator has been devised, similar to the above-described microwave method. This method utilizes the fact that the dielectric loss rate of water is about 13 (4 GHz, 25 ° C.), which is much larger than other materials. For example, a water-soluble material is applied on a film and a drying step is performed. It is used to manage a small amount of residual moisture later. In this method, by using a rectangular microwave cavity waveguide equipped with a slit at the center and a mechanism for holding the sheet-like sample in the slit, the resonance peak between when there is no sheet-like sample and when there is no sheet-like sample Moisture is measured from the difference in level (Patent Document 3). However, since this moisture measuring device (micro moisture meter) does not have a rotating mechanism, there is a problem that it cannot be used for measuring the degree of crystallinity that offsets the molecular orientation and anisotropy of the sample.

Japanese Patent Publication No. 02-029982 Japanese Patent No. 3334512 Japanese Patent No. 4321525

  As described above, with respect to molecular orientation, the microwave method using the above-described rectangular microwave cavity resonator has a problem that the structure of the measurement apparatus becomes complicated. Therefore, it has been a problem to easily rotate the sample so that the rotation angle can be positioned. In addition, regarding the crystallinity, in the method of measuring the crystallinity using a calibration curve from the dielectric loss rate by applying the microwave method, the rotation of the sample is used to measure the crystallinity with offsetting anisotropy. Since it is necessary to add a mechanism and the like, and there is a problem that the structure becomes complicated and expensive, it has been desired to measure the crystallinity simply and simply.

  In order to solve such problems, the inventors have devised a sample holder of a moisture measuring device using a rectangular microwave cavity resonator, a device (means) associated therewith, a shape of the moisture measuring device, and the like. Has devised a sample measuring device that can easily measure the degree of crystallinity that offsets molecular orientation and anisotropy.

  The sample measuring apparatus according to the first embodiment of the present invention can hold a microwave cavity resonator having a slit in a surface substantially perpendicular to the propagation direction of the microwave, a sheet-like sample, and can be inserted into the slit. A sample holding means; a locking means for locking the sample holding means at a predetermined position in the slit; and a measuring means for measuring a resonance frequency or a resonance peak level, and the sample inserted in the slit. When the holding means is rotated at a predetermined angle, the sample holding means can be locked at a predetermined position by the locking means.

  The sample holding means has a regular N-gon shape (N is an integer of 3 or more), and the locking means is formed to engage with at least a part of at least two sides of the regular N-gon shape. Can be.

  The microwave cavity resonator has a rectangular cross-sectional shape, and a hole portion larger than the rectangular cross-sectional shape is formed in the sample holding means, and the sheet-like sample covers the hole portion by the sample holding means. It can be held as follows.

  A sample measuring apparatus according to a second embodiment of the present invention includes a microwave cavity resonator provided with a slit in a surface substantially perpendicular to a microwave propagation direction, a sample mounting means for mounting a sheet-like sample, and the sample mounting A sample holding means that can be inserted into the slit and a measuring means for measuring a resonance frequency or a resonance peak level, and the sample attaching means is rotated when the sample attaching means is rotated at a predetermined angle. The means can be held by the sample holding means.

  Further, the microwave cavity resonator has a rectangular cross-sectional shape, the sample mounting means has a regular N-square shape larger than the rectangular cross-sectional shape, and the sample holding means is constituted by a pair of plates. Further, a hole having the same shape as the regular N-gon can be provided on one side, and a circular hole that is larger than the rectangular cross-sectional shape and smaller than the regular N-gon can be provided on the other side.

  Further, the sample mounting means can be held by being fitted into the regular N-shaped hole of the sample holding means.

  The sample measurement apparatus according to the third embodiment of the present invention is a microwave cavity resonator configured in the vertical direction by a pair of rectangular waveguides, and the propagation direction of the microwaves by the pair of rectangular waveguides. A microwave cavity resonator having a slit formed in a plane substantially perpendicular to the surface, and a sample stage on which a sheet-like sample is placed, storing the lower part of the rectangular waveguide, and on the bottom surface on the slit side The rectangular waveguide has a circular hole that is larger than the rectangular cross-sectional shape, and an angular scale is attached to the peripheral edge of the hole at a predetermined angle, and the sheet-like sample is placed so as to cover the hole. A sample stage configured to be placed, and a measuring unit that measures a resonance frequency or a resonance peak level, and the sheet-like sample can be rotated at the predetermined angle and placed on the sample stage. .

  Further, the sample measuring method by the sample measuring apparatus according to the first embodiment of the present invention includes a microwave cavity resonator having a slit on a surface substantially perpendicular to the propagation direction of the microwave, a sheet sample, Sample measurement comprising sample holding means insertable into the slit, locking means for locking the sample holding means at a predetermined position in the slit, and measuring means for measuring a resonance frequency or a resonance peak level A sample measurement method using an apparatus, the holding step for holding the sheet-like sample by the sample holding means, the locking step for locking the sample holding means at a predetermined position by the locking means, A measuring step of measuring a resonance frequency or a resonance peak level by a measuring means, and in the holding step, the sample holding means holding the sheet-like sample is set at a predetermined angle. By rolling, in each case, to implement said measurement step and the locking step.

  Further, the sample measuring method by the sample measuring apparatus according to the second embodiment of the present invention includes a microwave cavity resonator having a slit in a plane substantially perpendicular to the propagation direction of the microwave, and a sample attachment for attaching the sheet-like sample. A sample measuring method using a sample measuring apparatus comprising: a means; a sample holding means that holds the sample attaching means and can be inserted into the slit; and a measuring means that measures a resonance frequency or a resonance peak level. A sample attaching step for attaching the sheet-like sample by the sample attaching means; a holding step for holding the sample attaching means by the sample holding means; and the sample holding means for holding the sample attaching means in the holding step. A measuring step for measuring a resonance frequency or a resonance peak level by the insertion step of inserting into the slit and the measuring means. And a step, in the holding step, the sample mounting means holds is rotated at a predetermined angle, each time, to implement said measurement step and the inserted step.

  A sample measurement method using a sample measurement apparatus according to the third embodiment of the present invention is a microwave cavity resonator configured in a vertical direction by a pair of rectangular waveguides, and the pair of rectangular waveguides A microwave cavity resonator having a slit formed in a plane substantially perpendicular to the propagation direction of the microwave, and a sample stage on which a sheet-like sample is placed, and stores under the rectangular waveguide, The bottom surface on the slit side has a circular hole larger than the rectangular cross-sectional shape of the rectangular waveguide, and an angular scale is attached to the peripheral edge of the hole at a predetermined angle so as to cover the hole. A sample measuring method using a sample measuring device comprising a sample stage configured to place the sheet-like sample and a measuring means for measuring a resonance frequency or a resonance peak level, the sheet-like sample being the sample Perimeter of the hole in the base And a measuring step of measuring a resonance frequency or a resonance peak level by the measuring means, and the sheet-like sample is rotated at the predetermined angle each time. And the measurement step.

  According to the present invention, in a sheet-shaped sample measuring apparatus using a rectangular microwave cavity resonator, the molecular orientation is determined from the anisotropy of the dielectric constant of a sheet-shaped sample such as a polymer film, and the Q value (resonance sharpness). The crystallinity with the anisotropy canceled out can also be measured with a simple structure.

  Further, according to the present invention, it is possible to rotate the sample by placing the sheet-like sample in a state of good visibility in the slit of the rectangular microwave cavity resonator. It is possible to measure the degree of crystallinity that offsets orientation and anisotropy.

1 is a configuration diagram of a sample measurement system including a sample measurement device according to a first embodiment of the present invention. It is a schematic block diagram of the rectangular microwave cavity resonator of the sample measuring device which concerns on the 1st Embodiment of this invention. It is a figure of a sample holder and a stopper of a sample measuring device concerning a 1st embodiment of the present invention. It is a figure which shows the relationship between a dielectric loss rate and crystallinity. It is a schematic block diagram of the rectangular microwave cavity resonator of the sample measuring device which concerns on the 2nd Embodiment of this invention. It is a figure of the sample mounting plate and sample holder of the sample measuring device which concerns on the 2nd Embodiment of this invention. It is a figure which shows the molecular orientation of the sample measuring device which concerns on the 2nd Embodiment of this invention. It is a figure which shows the measurement result of the molecular orientation which concerns on the 2nd Example of this invention. It is a figure of the sample measuring device which concerns on the 3rd Embodiment of this invention. It is a figure which shows the measurement result of the molecular orientation based on the 3rd Example of this invention.

  Hereinafter, embodiments of the present invention will be described in detail.

(First embodiment)
FIG. 1 shows a configuration diagram of a sample measurement system 1 including a sample measurement device 10 according to the first embodiment of the present invention. The sample measurement system 1 mainly includes a sample measurement device 10, a network analyzer 20 provided outside the sample measurement device 10, and a computer 30.

  The sample measuring apparatus 10 includes a rectangular microwave air resonator inside thereof. The network analyzer 20 corresponds to the measurement unit of the present invention, and includes an oscillation unit that oscillates a microwave and a detection unit that detects resonance energy. The computer 30 processes a signal transmitted from the network analyzer 20. In FIG. 1, the network analyzer 20 is shown as a separate body from the sample measuring device 10, but the sample measuring device 10 may be integrated with the function of the network analyzer 20 to form the sample measuring device 10. . Moreover, the sample measuring device 10 can also measure a trace amount of water contained in the sample (that is, the sample measuring device 10 can also be applied to a moisture measuring device).

As shown in FIG. 2, the rectangular microwave cavity resonator 100 is composed of a pair of rectangular waveguides 102 (102A, 102B), and a slit (gap portion) 104 is formed on a surface substantially perpendicular to the microwave propagation direction. ing. Then, a sheet-like sample 106 obtained by molding a polymer resin such as PET (polyethylene terephthalate), which is a kind of polyester, into a sheet shape into the slit 104 is a regular N-square shape (see FIG. 3). In the example shown, it is a regular pentagon, and N is an integer of 3 or more. The sample holder 108 is inserted (inserted) after being held (after being attached by a mounting member (not shown) such as a tape). ) In the sample measuring apparatus 10, when the sample holder 108 is inserted into the inside of the sample measuring apparatus 10 (slit 104), a positive N which is the outer shape of the sample holder 108 for fixing and fixing the position thereof. A stopper (locking means) 110 is provided that is formed so that at least a part of at least two sides of the square is fitted and engaged. Further, in the present embodiment, as an example, the sample holder 108 is described as a regular N-gonal shape. However, as will be described later, the sheet sample can be fixed and rotated at a predetermined angle (for example, The shape is not limited to this as long as it is a star shape or the like. In this case, the stopper 110 is also formed in a shape that allows the sample holder 108 to be fitted and engaged to be locked.

  In addition, as shown in FIG. 3, the sample holder 108 has a rectangular cross-sectional shape of the rectangular waveguide 102 so that the microwave output from the rectangular waveguide 102 is directly irradiated to the sheet-like sample 106. A larger circular hole 112 is provided. The material of the sample holder 108 is preferably a material having a low dielectric constant in order to reduce the reflection of the microwave as much as possible and prevent the reflected wave from affecting the measurement value. Specifically, Teflon (registered trademark), polycarbonate, hard vinyl chloride, polyacetal, ultra high molecular weight polyethylene, MC nylon and the like are preferable. The same material can also be used in the sample holder of Embodiment 2 described later.

  The rectangular microwave cavity resonator 100 receives a microwave of 4 GHz band oscillated from the network analyzer 20 and is swept with a sweep width of about 100 MHz around the resonance frequency. The sweep is repeated about every 0.3 seconds, and the resonance peak frequency and the resonance peak level are detected and transmitted to the computer 30 each time.

The network analyzer 20 measures the Q value (resonance sharpness) in addition to the resonance frequency and the resonance peak level. Here, the relationship between the resonance peak level and the Q value is expressed by the following equation (1).
Δ (1 / Q) = (1 / Q ₀ ) · ((P ₀ / P _S ) ^0.5 −1) (1)
here,
Δ (1 / Q) = 1 / Q _S −1 / Q ₀ (2)
Q ₀ : Q value when there is no sample
Q _S : Q value when there is a sample
P ₀ : Resonance peak level before sample insertion
P _S : Resonance peak level after sample insertion

  The resonance peak level and the Q value shown in the above formula are both related to the absorption amount of the microwave energy in the sample. Specifically, the Q value is obtained by reducing the resonance frequency by half from the peak of the resonance curve (3 This is a value divided by the half bandwidth of the frequency at the level of decibel), and this corresponds to the ratio of the resonance energy stored in the rectangular microwave cavity resonator and the energy consumed inside the sample. Therefore, the greater the amount of microwave energy absorbed in the sample, the lower the resonance peak level and the Q value.

Here, the dielectric loss rate ε ″ can be obtained by the following equation.
ε ″ = (A / d) ((1 / Q _S ) − (1 / Q ₀ ) (3)
Q ₀ : Q value when there is no sample
Q _S : Q value when there is a sample
d: Sample thickness (mm)
A: Device constant

  Furthermore, the dielectric loss ratio ε ″ and the crystallinity have a first-order correspondence (as described in Patent Document 2), for example, as shown in the calibration curve of the PET film in FIG. Since the dielectric loss factor is large in the amorphous part (amorphous) and the dielectric loss factor is almost zero in the crystal part, it is generally shown in a negative proportional relationship.

  Accordingly, the crystallinity can be obtained by calculating the dielectric loss rate ε ″ from the sample thickness d and the Q value. Also, when comparing the crystallinity of materials having the same sample thickness, the Q value can be obtained. If only the measurement is performed, it is possible to instantaneously determine which crystallinity is higher by considering the relationship between the dielectric loss rate ε ″ and the crystallinity. That is, if the thickness of the sample is the same, the sample having a higher Q value has a higher crystallinity. Thus, instead of measuring the dielectric loss rate, it is possible to compare the crystallinity by measuring only the Q value.

  However, the dielectric loss rate is a material constant related to energy absorption based on molecular motion, and naturally changes depending on the frequency and temperature, and also generally changes depending on the direction when the sample is a polymer. In particular, when the sheet-like sample 106 is measured by a sample measuring apparatus such as the sample measuring apparatus 10, since the microwave electric field is applied in parallel to the surface direction of the sheet, the dielectric constant and dielectric loss depend on the molecular orientation (orientation). Anisotropy (direction dependence) appears in the rate. In this case, the Q value also changes depending on the direction in the sheet plane because of the relationship between the dielectric loss rate and the Q value. Therefore, in order to measure the crystallinity more accurately, it is necessary to cancel (cancel) the anisotropy of the Q value.

Therefore, the inventors considered to cancel the anisotropy of the Q value by rotating the sheet-like sample 106 at a constant angle and averaging the Q value measured at each angle. Specifically, the sample holder 108 is relatively rotated at a certain angle each time during measurement while holding the sheet-like sample 106, and the sample holder 108 is provided inside the sample measuring apparatus 10. By inserting the stopper 110 until it is engaged and locked, the rotational angle position is simply positioned, and the Q value is measured. Then, the measured Q value is averaged to cancel the anisotropy of the Q value. In this case, by increasing the number of Ns of regular N-gons, the rotation angle becomes finer, so that further improvement in accuracy can be expected.

  Specific examples of the first embodiment of the present invention will be described below.

(First embodiment)
In the first example, the crystallinity of the sheet-like sample 106 was compared using the Q value in the configuration as shown in FIG. As described above, the crystallinity has a correlation with the Q value. If the thickness is the same, the crystallinity increases as the Q value increases. As the sheet-like sample 106, a commercially available PET film A (thickness: 100 μm) is held so that the hole 112 is covered with a regular pentagonal sample holder 108 as shown in FIG. 3, and a stopper 110 is inserted from the insertion port of the sample measuring device 10. The Q value was measured by the network analyzer 20 after being inserted up to the position where it was locked.

Q value at this time is measured as 5193 and its value as Q _1. Next, the sample holder 108 is once taken out from the sample measuring apparatus 10 and rotated in the direction of 72 degrees while holding the sheet-like sample 106 (for example, from “A” to “B” in FIG. 3). The sample was again inserted from the insertion port of the sample measuring device 10 to the position locked by the stopper 110, and the Q value was measured. Q value at this time is measured as 5172 and its value and Q _2. When the sample holder 108 was rotated in the same procedure and measurement was performed on Q ₃ , Q ₄ , and Q ₅ , Q ₃ was measured as 5185, Q ₄ as 5214, and Q ₅ as 5181. In this case, the average value of Q ₁ , Q ₂ , Q ₃ , Q ₄ , and Q ₅ was 5189.

Next, regarding the PET film B having the same thickness (100 μm thickness) as the PET film A, the Q value was measured in the same manner as the PET film A, and the average value was calculated. As a result, Q ₁ , Q ₂ , Q ₃ , Q The average value of ₄ and Q ₅ was 5073. From this, it was found that the average value of the Q values of the PET film A was larger than the average value of the Q values of the PET film B, and the PET film A had a higher crystallinity than the PET film B.

(Second Embodiment)
In the present embodiment, as shown in FIG. 5, the molecular orientation of the sheet-like sample 126 is changed using the rectangular microwave cavity resonator 120 having the same configuration as the rectangular microwave cavity resonator 100 of the first embodiment described above. taking measurement. Conventionally, the molecular orientation has been measured from the anisotropy of the refractive index, and in the high frequency range, the refractive index and the dielectric constant are caused by the same electronic polarization, and the square of the refractive index corresponds to the dielectric constant. The molecular orientation can also be measured from the dielectric anisotropy.

  In the measurement of molecular orientation based on the anisotropy of the refractive index, the direction in which the refractive index is maximum is the direction in which the molecular chains are arranged, and the degree of anisotropy is birefringence Δn (difference between the maximum and minimum refractive indices). ). Similarly, in the measurement of molecular orientation based on the anisotropy of dielectric constant, the direction in which the dielectric constant is maximum is the direction in which molecular chains are arranged, and the degree of anisotropy is Δε (maximum and minimum of dielectric constant). Difference).

  In the present embodiment, when the sheet-like sample 126 is inserted into the slit 124 of the rectangular microwave cavity resonator 120, the resonance frequency is shifted to the low frequency side. This shift amount Δf is equal to the thickness of the sheet-like sample 126. It is proportional to the product of dielectric constant. Therefore, the molecular orientation can be confirmed by calculating the shift amount Δf. However, since this dielectric constant corresponds to the dielectric constant of the electric field direction (electric field propagation direction) in the rectangular microwave cavity resonator 120, in order to obtain the shift amount Δf corresponding to the dielectric constant in all directions, Either the rectangular microwave cavity resonator 120 or the sheet sample 126 needs to be rotated.

Therefore, in this embodiment, as shown in FIG. 6, hard vinyl chloride, produced like polycarbonate, sample outline positive N polygon (in regular octagon in the example shown in FIG. 6, N is an integer of 3 or more) After the sheet-like sample 126 is attached to the attachment plate 130 (130A) with an attachment member 132 such as a tape and sandwiched from both sides by the sample attachment plates 130A and 130B , the sample attachment plate 130 as the sample attachment means is used at the time of measurement. In each case, the sheet-like sample 126 is rotated by relatively rotating and holding the sample mounting plate 130 by the sample holder 128 (128A). As shown in FIG. 6, the sample holder 128 is composed of a pair of resin plates of an upper part 128A and a lower part 128B, and the regular N-shaped hole 134 of the upper part 128A of the sample holder 128 is a rectangular waveguide 122. The rectangular cross-sectional shape of the rectangular waveguide 122 is larger than the rectangular cross-sectional shape of the rectangular waveguide 122, and the positive N of the upper portion 128A is formed in the lower portion 128B. A circular hole 136 smaller than the square hole 134 is formed. Further, the sample mounting plate 130 is fitted (fitted) into a regular N-shaped hole 134 formed on the upper part 128A side of the sample holder 128 in which the upper part 128A and the lower part 128B are combined. Retained. In this way, by rotating the sample mounting plate 130 (sheet sample 126) and measuring the resonance frequency, the resonance frequency shift amount Δf is calculated for each.

Then, the calculated shift amount Δf is plotted on polar coordinates, and an elliptical approximation is performed to obtain an elliptical pattern as shown in FIG. In FIG. 7, the maximum direction of the major axis of the ellipse is the direction where the dielectric constant is maximum, that is, the direction in which molecular chains are arranged. The degree of orientation can be expressed by the ratio or difference between the major axis and minor axis of the elliptic pattern shown in FIG.
The dielectric constant is calculated using the following equation.
ε ′ = 1 + (A / d) (f1−f2) / (f1−γ) (4)
F1: Resonance frequency (MHz) when there is no sample
f2: Resonance frequency when there is a sample (MHz)
γ: Gap correction value (MHz)
d: Sample thickness (mm)
A: Device constant

Specific examples of the second embodiment of the present invention will be described below.
(Second embodiment)
In the configuration as shown in FIG. 1, the molecular orientation of the sheet-like sample 126 was measured. First, as shown in FIG. 6 described above, the sample mounting plate 130 is aligned with the regular octagonal hole 134 from above the rectangular sample holder 128 without mounting the sheet-like sample 126 on the regular octagonal sample mounting plate 130. The sample holder 128 and the sample mounting plate 130 were inserted into the sample measuring apparatus 10 in an integrated state. In this state, the network analyzer 20 was used to measure the resonance frequency when the sheet-like sample 126 was not inserted (that is, when blank). Then, the measured value was defined as f _0.

Next, the reference direction of the sheet-like sample 126 to be measured is determined, and the sheet is attached to the regular octagonal sample attachment plate 130, which is the same as the sample attachment plate 130 used for the measurement at the time of blanking, with a tape (attachment member) 132. With the sample 126 attached and clamped from both sides, the sample mounting plate 130 is fitted into the regular octagonal hole 134 from above the sample holder 128, and the sample holder 128, the sample mounting plate 130 and the sheet sample 126 are integrated. In the state, it was inserted into the sample measuring apparatus 10. In this state, the network analyzer 20 was used to measure the resonance frequency when the sheet-like sample 126 was inserted. This measured value was defined as f _s1 .

Further, the sample holder 128 was taken out from the sample measuring apparatus 10, the regular octagonal sample mounting plate 130 was rotated 45 degrees with respect to the reference direction, and fitted again into the sample holder 128, and similarly the resonance frequency was measured. This measured value was defined as f _s2 . Similarly, the sample mounting plate 130 was rotated 45 degrees to measure up to f _s3 and f _s4 , and the resonance frequency shift amount Δf was calculated for each.

Note that the shift amount Delta] f of the resonance frequency is the difference between the resonance frequency f _s in a state where the resonance frequency f ₀ and the sheet-like sample 126 during the blank is inserted into the sample measuring apparatus _{10 (Δf = f 0 -f s} ) expressed. This was calculated from _{Δf s1 (Δf s1 = f 0} -f s1) to _{Δf s4 (Δf s4 = f 0} -f s4), Δf s1, Δf s2, Δf s3, a Delta] f _s4 as a point, on the polar coordinate Plotted. In the second embodiment, when Δf _s5 , Δf _s6 , Δf _s7 , Δf _s8 are calculated in the same manner, Δf _s5 , Δf _s6 , Δf _s7 , Δf _s8 are Since calculation is performed at positions that are symmetrical with respect to Δf _s1 , Δf _s2 , Δf _s3 , and Δf _s4 , they are plotted at the calculated positions. The above eight points Δf are plotted on the polar coordinates and subjected to ellipse approximation to obtain molecular orientation as shown in FIG. In the molecular orientation shown in FIG. 8, the orientation angle could be calculated as the angle between the reference direction and the major axis of the ellipse, and the orientation degree could be calculated as the ratio of the major axis to the minor axis.

(Third embodiment)
As described above, by measuring the Q value for samples having the same thickness, the crystallinity can be easily compared. However, in order to compare the crystallinity more accurately (that is, anisotropic) In order to offset the above and compare the crystallinity), it is necessary to rotate the sheet-like sample at a predetermined angle, measure the Q value, and take the average. Also, when measuring the molecular orientation of a sheet-like sample from the difference (shift amount) between the resonance frequency when the sheet-like sample is not inserted into the measuring apparatus and the resonance frequency when it is inserted, the sheet-like sample is measured at a predetermined angle. Need to rotate.

  Therefore, in the present embodiment, a sample measuring apparatus that can easily rotate a sample manually without providing a rotation mechanism such as a motor will be described. As shown in FIG. 9, the sample measurement device 11 stores one of the rectangular waveguides 142 (downward in FIG. 9) that constitutes the rectangular microwave cavity resonator 140 in the vertical direction, and microwaves. A sample stage 152 having a circular hole 150 larger than the rectangular cross-sectional shape of the rectangular waveguide 142 is installed on the bottom surface on the slit 144 side formed in a plane substantially perpendicular to the propagation direction of An angular scale 156 is attached to the peripheral edge 154 of the hole 150 so that the operator can rotate and place the sheet-like sample 146 based on an arbitrary angle while checking the sheet-like sample 146. To do. Thus, when measuring the crystallinity, the Q value is measured while rotating the sheet-like sample 146 at a predetermined angle, and the average is calculated to easily cancel the anisotropy of the Q value. be able to. When measuring the molecular orientation, the resonance frequency is measured while rotating the sheet-like sample 146 by a predetermined angle, and the resonance frequency measured without the sheet-like sample 146 being placed on the sample stage 152 The molecular orientation can be easily measured from the anisotropy of the difference (shift amount). Furthermore, since the sheet-like sample 146 can be placed on the sample stage 152, the measurement can be performed with good visibility. The sheet-like sample 146 is formed in a circle so as to follow the shape of the peripheral edge 154 of the circular hole 150 in order to be placed on the peripheral edge 154 of the circular hole 150. It is preferable that a mark that can be aligned with the angle scale 156 is attached. In FIG. 9, a housing (case) 158 that houses the rectangular waveguide 142 positioned above is formed in an inverted triangular shape so that the angle scale 156 can be visually recognized at the time of measurement.

  Hereinafter, specific examples of the third embodiment of the present invention will be described.

(Third embodiment)
The molecular orientation of the sheet-like sample 146 was measured using the sample measuring device 11 provided with the sample stage 152 as shown in FIG. In addition, as the sample stage 152, the one provided with an angular scale every 30 degrees on the peripheral edge 154 of the circular hole 150 is used. First, a sheet-like sample 146 measured resonance frequency in a state that is not placed on the sample stage 152, and the resonant frequency f _0. Next, a commercially available PET film (sample) is cut into a circle, and a mark is attached in the reference direction. An angle scale 156 from 0 degrees to 360 degrees drawn on the sample table 152 as a sheet-like sample 146 is obtained. It was mounted according to the 0 degree direction. Then, using this state as a starting point, the resonance frequency is measured, and when the measurement is completed, the sheet-like sample 146 is rotated 30 degrees, and the mark attached to the sheet-like sample 146 is placed so as to coincide with the scale position of 30 degrees. did.

The resonance frequency is measured in a state rotated by 30 degrees, and after the measurement is completed, the sheet-like sample 146 is further rotated by 30 degrees, and the sheet-like sample 146 is placed on the sample stage 152 to measure the resonance frequency. This procedure was repeatedly executed, and resonance frequencies f _s1 to f _s6 at six points from 0 degree to 150 degrees were measured. From this result, the shift amount Δf of the resonance frequency at each angle was calculated, and Δf1 to Δf6 were obtained. Furthermore, by plotting these (also Δf7 to Δf12 calculated as point-symmetric with respect to the origin position) on polar coordinates and applying elliptical approximation in the same manner as in the second embodiment, an elliptical pattern as shown in FIG. 10 is obtained. I got it. In FIG. 10, the molecular orientation of the sheet-like sample 146 could be easily measured so that the major axis direction is the orientation direction and the ratio of the major axis to the minor axis is indicated as the degree of orientation.

  The industrial application fields of the present invention include industrial application fields of sheet-like materials such as polymer film manufacturing and research and development fields, and new material manufacturing and research and development fields using polymer films.

DESCRIPTION OF SYMBOLS 1 Sample measuring system 10 Sample measuring apparatus 11 Sample measuring apparatus 20 Network analyzer 30 Computer 100 Rectangular microwave cavity resonator 102 Rectangular waveguide 104 Slit (gap part)
106 Sheet Sample 108 Sample Holder 110 Stopper 112 Circular Hole 120 Rectangular Microwave Cavity Resonator 122 Rectangular Waveguide 124 Slit (Gap)
126 Sheet Sample 128 Sample Holder 130 Sample Mounting Plate 132 Mounting Member 134 Regular N Square Hole 136 Circular Hole 140 Rectangular Microwave Cavity Resonator 142 Rectangular Waveguide 144 Slit (Gap)
146 Sheet Sample 150 Circular Hole 152 Sample Stand 154 Perimeter 156 Angle Scale 158 Housing (Case)

Claims (8)

A microwave cavity resonator having a slit in a plane substantially perpendicular to the propagation direction of the microwave;
A sample holding means for holding a sheet-like sample and being insertable into the slit;
In the slit, locking means for fitting the outer shape of the sample holding means to lock the sample holding means at a predetermined relative rotation position ;
A measuring means for measuring the resonance frequency or the resonance peak level;
With
When the sample holding means inserted in the slit is rotated at a predetermined angle, the sample holding means can be fitted to the locking means and locked at a predetermined relative rotation position. A sample measuring device characterized by the above. The sample holding means has a regular N-gon shape (N is an integer of 3 or more),
The sample measuring apparatus according to claim 1, wherein the locking unit is formed to engage with at least a part of at least two sides of the regular N-gon. The microwave cavity resonator has a rectangular cross-sectional shape;
3. A hole portion larger than the rectangular cross-sectional shape is formed in the sample holding means, and the sheet-like sample is held by the sample holding means so as to cover the hole portion. Sample measuring device. A microwave cavity resonator having a slit in a plane substantially perpendicular to the propagation direction of the microwave;
A sample attaching means for attaching a sheet-like sample;
A sample holding means that can be fitted into the outer shape of the sample mounting means to hold the sample mounting means at a predetermined relative rotational position and can be inserted into the slit;
A measuring means for measuring the resonance frequency or the resonance peak level;
With
A sample measuring apparatus characterized in that when the sample mounting means is rotated at a predetermined angle, the sample mounting means can be fitted to the sample holding means and held at a predetermined relative rotational position. . The microwave cavity resonator has a rectangular cross-sectional shape;
The sample mounting means has a regular N-gon shape larger than the rectangular cross-sectional shape,
The sample holding means is composed of a pair of plates, one having a hole having the same shape as the regular N square, and the other having a circular hole smaller than the regular N square hole and larger than the rectangular cross-sectional shape. The sample measuring apparatus according to claim 4, further comprising a portion.   6. The sample measuring apparatus according to claim 5, wherein the sample mounting means is held by being fitted into the regular N-shaped hole of the sample holding means. A microwave cavity resonator having a slit in the propagation direction substantially perpendicular to the plane of the microwave, and holding the sheet-like sample, and the sample holding means which can inserted into the slit in the slit, the sample holding means A sample measuring method using a sample measuring device comprising: a locking unit that fits the outer shape to lock the sample holding unit at a predetermined relative rotational position; and a measuring unit that measures a resonance frequency or a resonance peak level.
A holding step of holding the sheet-like sample by the sample holding means;
A locking step of locking the sample holding means by fitting with the locking means in a predetermined relative rotational position,
A measuring step of measuring a resonance frequency or a resonance peak level by the measuring means;
Including
In the holding step, the sample holding means holding the sheet-like sample is rotated at a predetermined angle, and the locking step and the measuring step are performed each time. A microwave cavity resonator having a slit in a plane substantially perpendicular to the propagation direction of the microwave, a sample attachment means for attaching a sheet-like sample, and the sample attachment means are fitted to the outer shape of the sample attachment means so that the sample attachment means has a predetermined relative A sample measurement method using a sample measurement device comprising a sample holding means that is held at an angle and can be inserted into the slit, and a measurement means that measures a resonance frequency or a resonance peak level,
A sample attaching step of attaching the sheet-like sample by the sample attaching means;
A holding step of fitting the sample mounting means to the sample holding means to hold the sample mounting means at a predetermined relative rotational position ;
In the holding step, an insertion step of inserting the sample holding means holding the sample mounting means into the slit;
A measuring step of measuring a resonance frequency or a resonance peak level by the measuring means;
Including
In the holding step, the sample mounting means is rotated and held at a predetermined angle, and the inserting step and the measuring step are performed each time.

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