Method for measuring fiber orientation degree, fiber orientation degree measurement apparatus, and control computer program for fiber orientation degree measurement apparatus
11360035 · 2022-06-14
Assignee
- National University Corporation Tokai National Higher Education And Research System (Nagoya, JP)
- Toray Industries, Inc. (Tokyo, JP)
- KYOWA INDUSTRIAL CO., LTD. (Sanjo, JP)
Inventors
- Atsuhiko Yamanaka (Aichi, JP)
- Mariko Terada (Aichi, JP)
- Yukitane Kimoto (Aichi, JP)
- Koji SHIRAKI (Shizuoka, JP)
- Yuji Hotta (Aichi, JP)
- Daisuke Shimamoto (Aichi, JP)
Cpc classification
International classification
Abstract
A method for measuring a fiber orientation degree includes: irradiating a sample formed of a composite material containing discontinuous carbon fibers with an X-ray to acquire an X-ray diffraction image; calculating an angle (2θ).sub.A of a peak originating from a crystal face of graphite; calculating a correction coefficient δ of a thickness of the sample; calculating an upper limit (2θ).sub.B of the peak of the crystal face of graphite; calculating a diffraction sensitivity I.sub.C(ϕ) of the peak originating from the crystal face of graphite by correcting an integrating range with the correction coefficient δ and integrating the X-ray diffraction image with respect to a diffraction angle (2θ); and calculating a fiber orientation degree Sd(β) by the method of Hermans from the diffraction sensitivity I.sub.C(ϕ).
Claims
1. A method for measuring a fiber orientation degree comprising: a diffraction image acquisition process of irradiating a sample formed of a composite material containing discontinuous carbon fibers with an X-ray to acquire an X-ray diffraction image; a peak angle calculation process of calculating an angle (2θ).sub.A of a peak originating from a crystal face of graphite from an inflection point A of an integral value I(2θ) obtained by integrating the X-ray diffraction image with respect to an azimuth angle (ϕ); a correction coefficient calculation process of calculating a correction coefficient δ of a thickness of the sample; an upper limit calculation process of calculating an upper limit (2θ).sub.B of the peak of the crystal face of graphite from an inflection point B of the integral value I(2θ); a diffraction sensitivity calculation process of calculating a diffraction sensitivity I.sub.C(ϕ) of the peak originating from the crystal face of graphite by correcting an integrating range with the correction coefficient δ and integrating the X-ray diffraction image with respect to a diffraction angle (2θ); and an orientation degree calculation process of calculating a fiber orientation degree Sd(β) by the method of Hermans from the diffraction sensitivity I.sub.C(ϕ), wherein the correction coefficient calculation process includes calculating the correction coefficient δ by Formula (1) below:
δ=(2θ).sub.A−tan.sup.−1{(1−t/L).Math.tan(2θ).sub.A} (1) in Expression (1), t indicates a thickness (mm) of the sample, and L indicates a distance (mm) from an incident plane of the X-ray of the sample to a film surface on which the X-ray diffraction image is projected.
2. The method for measuring a fiber orientation degree according to claim 1, wherein the diffraction sensitivity calculation process includes setting an angular integrating range to be from (2θ).sub.A−δ to (2θ).sub.A+δ when (2θ).sub.A+δ>(2θ).sub.B and setting the angular integrating range to be from (2θ).sub.A−δ to (2θ).sub.B when (2θ).sub.A+δ≤(2θ).sub.B.
3. The method for measuring a fiber orientation degree according to claim 1, wherein the diffraction sensitivity calculated at the diffraction sensitivity calculation process is a sum of diffraction sensitivities of crystal faces [002], [004], and [006] of graphite.
4. The method for measuring a fiber orientation degree according to claim 1, wherein the orientation degree calculation process includes calculating the fiber orientation degree Sd(β) by Expressions (2), (3), and (4) below:
S.sub.0=∫.sub.−π/2(−90°).sup.+π/2(+90°)I.sub.C(ϕ)dϕ (2)
S.sub.1(β)=∫.sub.−π/2(−90°).sup.+π/2(+90°)I.sub.C(ϕ).Math.cos.sup.2βdϕ.sub.0 (3) in Expression 3, β=ϕ−ϕ.sub.0,
Sd(β)=(3.Math.S.sub.1(β)/S.sub.0−1)/2 (4).
5. A fiber orientation degree measurement apparatus comprising: an X-ray diffraction imaging system including an X-ray irradiator configured to irradiate a sample formed of a composite material containing discontinuous carbon fibers with an X-ray to acquire an X-ray diffraction image; and a CPU programmed to function as: a peak angle calculation unit configured to calculate an angle (2θ).sub.A of a peak originating from a crystal face of graphite from an inflection point A of an integral value I(2θ) obtained by integrating the X-ray diffraction image with respect to an azimuth angle (ϕ); a correction coefficient calculation unit configured to calculate a correction coefficient δ of a thickness of the sample; an upper limit calculation unit configured to calculate an upper limit (2θ).sub.B of the peak of the crystal face of graphite from an inflection point B of the integral value I(2θ); a diffraction sensitivity calculation unit configured to calculate a diffraction sensitivity I.sub.C(ϕ) of the peak originating from the crystal face of graphite by correcting an integrating range with the correction coefficient δ and integrating the X-ray diffraction image with respect to a diffraction angle (2θ); and an orientation degree calculation unit configured to calculate a fiber orientation degree Sd(β) by the method of Hermans from the diffraction sensitivity I.sub.C(ϕ), wherein the CPU is further configured to calculate the correction coefficient δ by Formula (1) below:
δ=(2θ).sub.A−tan.sup.−1{(1−t/L).Math.tan(2θ).sub.A} (1) in Expression (1), t indicates a thickness (mm) of the sample, and L indicates a distance (mm) from an incident plane of the X-ray of the sample to a film surface on which the X-ray diffraction image is projected.
6. A non-transitory computer-readable recording medium with an executable program stored thereon, the program being a control program for a fiber orientation degree measurement apparatus executing: a diffraction image acquisition procedure of irradiating a sample formed of a composite material containing discontinuous carbon fibers with an X-ray to acquire an X-ray diffraction image; a peak angle calculation procedure of calculating an angle (2θ).sub.A of a peak originating from a crystal face of graphite from an inflection point A of an integral value I(2θ) obtained by integrating the X-ray diffraction image with respect to an azimuth angle (ϕ); a correction coefficient calculation procedure of calculating a correction coefficient δ of a thickness of the sample; an upper limit calculation procedure of calculating an upper limit (2θ).sub.B of the peak of the crystal face of graphite from an inflection point B of the integral value I(2θ); a diffraction sensitivity calculation procedure of calculating a diffraction sensitivity I.sub.C(ϕ) of the peak originating from the crystal face of graphite by correcting an integrating range with the correction coefficient δ and integrating the X-ray diffraction image with respect to a diffraction angle (2θ); and an orientation degree calculation procedure of calculating a fiber orientation degree Sd(β) by the method of Hermans from the diffraction sensitivity I.sub.C(ϕ), wherein the correction coefficient calculation procedure includes calculating the correction coefficient δ by Formula (1) below:
δ=(2θ).sub.A−tan.sup.−1{(1−t/L).Math.tan(2θ).sub.A} (1) in Expression (1), t indicates a thickness (mm) of the sample, and L indicates a distance (mm) from an incident plane of the X-ray of the sample to a film surface on which the X-ray diffraction image is projected.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
DESCRIPTION OF EMBODIMENTS
(14) The following describes a method for measuring a fiber orientation degree, a fiber orientation degree measurement apparatus, and a control program for a fiber orientation degree measurement apparatus of the present invention with reference to the accompanying drawings.
(15)
(16) The diffraction image acquisition unit 10 irradiates sample formed of a composite material containing discontinuous carbon fibers with an X-ray to acquire an X-ray diffraction image (a Debye ring). With measurement of a fiber orientation degree of the discontinuous carbon fibers in the composite material as an object, and with CFRP mainly containing discontinuous carbon fibers and a matrix resin as a sample, the fiber orientation degree measurement apparatus 100 of the present invention acquires the X-ray diffraction image using a characteristic X-ray such as the Cu-Kα line. The fiber orientation degree measurement apparatus 100 of the present invention is suitable for measurement of an orientation degree of the discontinuous carbon fibers in CFRP and can also be used for measurement of a fiber orientation degree in a mat formed of discontinuous carbon fibers containing no matrix resin. The discontinuous carbon fibers may be any of PAN-based and pitch-based carbon fibers. The matrix resin can be the sample of the present invention when any of a thermosetting resin, a thermoplastic resin, and a resin containing both a thermosetting resin and a thermoplastic resin is used so long as they are resins used for CFRP.
(17) As illustrated in
(18) The controller 20 has a peak angle calculation unit 21, a correction coefficient calculation unit 22, an upper limit calculation unit 23, a diffraction sensitivity calculation unit 24, and an orientation degree calculation unit 25. The controller 20 is implemented by using a central processing unit (CPU) executing various kinds of processing programs, a read only memory (ROM) storing therein the various kinds of processing programs and the like in advance, and a random access memory (RAM) storing therein an arithmetic orientation degree of each processing and the like. As the controller 20, a general-purpose computer such as a work station or a personal computer can be used.
(19) The peak angle calculation unit 21 extracts a diffraction pattern with a certain azimuth angle (ϕ) from the X-ray diffraction image acquired by the diffraction image acquisition unit 10 and calculates an angle (2θ).sub.A of a peak originating from a crystal face of graphite from an inflection point of an integral value of the diffraction pattern.
(20) As illustrated in
(21)
(22) The peak angle calculation unit 21 integrates the X-ray diffraction image in
I(2θ)=∫.sub.−π/2(−90°).sup.+π/2(+90°)I(2θ,ϕ)dϕ (5)
(23) In Expression (5), the reason why the integrating range is from −π/2 (−90°) to +π/2 (+90°) is to exclude the influence of a shadow projected on the X-ray diffraction image. When no shadow is projected on the X-ray diffraction image depending on the used apparatus, the X-ray diffraction image may be integrated from −π (−180°) to +π (+180°).
(24)
(25) The peak angle (2θ).sub.A originating from the [002] face can be determined by referring to the diffraction angle 2θ (25.9 to 26.6°) of the crystal face [002] of general graphite illustrated in
(26) The correction coefficient calculation unit 22 calculates a correction coefficient δ of a thickness t (mm) of the sample. The correction coefficient δ can be calculated by Expression (1) below.
δ=(2θ).sub.A−tan.sup.−1{(1−t/L).Math.tan(2θ).sub.A} (1)
(27) In Expression (1), t indicates the thickness (mm) of the sample, and L indicates a distance (mm) from an incident plane of the X-ray of the sample to a film surface on which the X-ray diffraction image is projected.
(28) The diffraction angle (2θ) on the horizontal axis of the diffraction pattern in
(29) The upper limit calculation unit 23 calculates an upper limit (2θ).sub.B of the peak originating from the crystal face of graphite from an angle (2θ).sub.B of an inflection point B of the integral value I(2θ) obtained by integrating the X-ray diffraction image with respect to the azimuth angle (ϕ). The upper limit (2θ).sub.B of the peak is an upper limit of an integrating range when the diffraction sensitivity calculation unit 24 described below integrates the diffraction sensitivity I(2θ, ϕ) with respect to the diffraction angle (2θ) to calculate a diffraction sensitivity I.sub.C(ϕ) of the peak of the crystal face of graphite.
(30)
(31) The diffraction sensitivity calculation unit 24 calculates the diffraction sensitivity I.sub.C(ϕ) of the peak originating from the crystal face of graphite by correcting the integrating range with the correction coefficient δ calculated by the correction coefficient calculation unit 22 and integrating the X-ray diffraction image with respect to the diffraction angle (2θ).
(32) With a value (2θ).sub.A−δ obtained by subtracting the correction coefficient δ from the angle (2θ).sub.A of the peak of the crystal face [002] of graphite as the lower limit of the integrating range and with (2θ).sub.B calculated by the upper limit calculation unit 23 as the upper limit, the peak sensitivity I.sub.002(ϕ) of the crystal face [002] of graphite can be calculated by Expression (6) below.
I.sub.002(ϕ)=∫.sub.(2θ).sub.
(33) Depending on the correction coefficient δ, a value (2θ).sub.A+δ obtained by adding the correction coefficient δ to the angle (2θ).sub.A of the peak of the crystal face [002] of graphite may be a value larger than (2θ).sub.B. In such a case, the peak sensitivity I.sub.002(ϕ) of the crystal face [002] of graphite may be calculated by Expression (7) below with (2θ).sub.A−δ as the lower limit and with (2θ).sub.A+δ as the upper limit.
I.sub.002(ϕ)=∫.sub.(2θ).sub.
(34) The diffraction image acquisition unit 10 illustrated in
I.sub.C(ϕ)=I.sub.002(ϕ)+I.sub.004(ϕ)+I.sub.006(ϕ) (8)
(35) Alternatively, the diffraction sensitivity I.sub.002(ϕ) at the crystal face [002] of graphite is the largest, and the diffraction sensitivity I.sub.002(ϕ) may be regarded as the diffraction sensitivity I.sub.C(ϕ).
(36) The orientation degree calculation unit 25 calculates the fiber orientation degree Sd(β) by the method of Hermans from the diffraction sensitivity I.sub.C(ϕ).
(37) The fiber orientation degree Sd(β) is an indicator indicating a level of presence in each direction at which the discontinuous carbon fibers are oriented within the sample and is calculated using Expressions (2), (3), and (4) below by the method of Hermans in the present invention.
S.sub.0=∫.sub.−π/2(−90°).sup.+π/2(+90°)I.sub.C(ϕ)dϕ (2)
S.sub.1(β)=∫.sub.−π/2(−90°).sup.+π/2(+90°)I.sub.C(ϕ).Math.cos.sup.2βdϕ.sub.0 (3)
(38) In Expression (3), β=ϕ−ϕ.sub.0.
Sd(β)=(3.Math.S.sub.1(β)/S.sub.0−1)/2 (4)
(39) As shown in Expression (9) below, a maximum value Sd.sub.0 of Sd(β) determined by Expression (4) is a fiber orientation degree Sd.sub.0 of the sample.
Sd.sub.0=max.Math.Sd(β) (9)
(40) As shown in Expression (10) below, β when Sd(β) is the maximum value Sd.sub.0 is β.sub.0.
β.sub.0=β|max.Math.Sd(β) (10)
(41) The crystal faces [002] and the like of graphite deviate from the direction of a principal axis of the carbon fibers by 90°, and a principal orientation angle α.sub.0 of the discontinuous carbon fibers is as Expression (11) below.
α.sub.0=β.sub.0±π/2 (11)
(42)
(43) The fiber orientation degree Sd(β) of the discontinuous carbon fibers in the sample is measured by the process of a flowchart illustrated in
(44) First, the diffraction image acquisition unit 10 acquires an X-ray diffraction image of the sample (Step S1), and the peak angle calculation unit 21 calculates the angle (2θ).sub.A of the peak originating from the crystal face of graphite from the inflection point A of the integral value I(2θ) obtained by integrating the X-ray diffraction image with respect to the azimuth angle (ϕ) (Step S2). The crystal face of graphite for which the angle (2θ).sub.A is calculated may be [002], [004], and [006] or only [002].
(45) Subsequently, the correction coefficient calculation unit 22 calculates the correction coefficient δ of the thickness of the sample (Step S3). The correction coefficient δ may be calculated from Expression (2).
(46) Subsequently, the upper limit calculation unit 23 calculates the upper limit (2θ).sub.B of the peak of the crystal face of graphite from the inflection point B of the integral value I(2θ) obtained by integrating the X-ray diffraction image with respect to the azimuth angle (ϕ) (Step S4). The inflection point B is a next inflection point above the angle (2θ).sub.A of the peak originating from the crystal face of graphite.
(47) After the upper limit (2θ).sub.B of the peak is calculated (Step S4), the diffraction sensitivity calculation unit 24 corrects the integrating range with the correction coefficient δ calculated at Step S3 (Step S5) and integrates the X-ray diffraction image with the integrating range calculated at Step S5 to calculate the diffraction sensitivity I.sub.C(ϕ) of the peak originating from the crystal face of graphite (Step S6). The integrating range is from (2θ).sub.A−δ to (2θ).sub.B when (2θ).sub.B≥(2θ).sub.A+δ and from (2θ).sub.A−δ to (2θ).sub.B when (2θ).sub.B<(2θ).sub.A+δ.
(48) After the diffraction sensitivity I.sub.C(ϕ) is calculated (Step S6), the orientation degree calculation unit 25 calculates the fiber orientation degree Sd(β) by the method of Hermans from the diffraction sensitivity I.sub.C(ϕ) (Step S7). The orientation degree calculation unit 25 outputs the maximum value Sd.sub.0 of the fiber orientation degree Sd(β) and the principal orientation angle α.sub.0 to the controller 20.
(49) The controller 20 performs control to display the maximum value Sd.sub.0 of the fiber orientation degree Sd(β) and the principal orientation angle α.sub.0 on the display unit 30 (Step S8).
(50) The present invention uses Expression (8) so that fiber orientation not only in the in-plane direction of the sample but also in the direction of the thickness t is taken into account for calculation of the fiber orientation degree Sd(β). With this consideration, the fiber orientation degree Sd(β) of a sample in which fiber orientation varies in the direction of the thickness t can be measured more accurately.
REFERENCE SIGNS LIST
(51) 10 Diffraction image acquisition unit 20 Controller 21 Peak angle calculation unit 22 Correction coefficient calculation unit 23 Upper limit calculation unit 24 Diffraction sensitivity calculation unit 25 Orientation degree calculation unit 30 Display unit 100 Fiber orientation degree measurement apparatus