Temperature Change of Orientation Function of Polymer Crystals Evaluated by the Simultaneous DSC-XRD and DSC-FTIR Methods

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1 Netsu Sokutei Temperature Change of Orientation Function of Polymer Crystals Evaluated by the Simultaneous DSC-XRD and DSC-FTIR Methods Takeshi Yamada, Takafumi Watanabe, and Hirohisa Yoshida (Received April 10, 2003; Accepted August 6, 2003) Temperature changes of orientation functions for uniaxial drawn polypropylene (ipp) were evaluated by the simultaneous DSC-XRD and DSC-FTIR methods. In order to evaluate the orientation function with high time resolution, two-dimensional CCD detector and MCT detector were used for XRD and FTIR measurements, respectively. The crystallographic and conformational orientation functions of crystal c-axis were obtained from two-dimensional XRD profiles and polarized FTIR spectra, respectively. The uniaxial drawn polypropylene showed the melting peak with a shoulder at lower temperature side. The crystallographic orientation function of c-axis decreased and the conformational orientation function of c-axis increased at temperature below the melting. This fact suggested that the melt-recrystallization was brought into the re-organization of drawn ipp. 1-3) S 4) S S pos S or S conf (1) S pos S conf S or 5) DSC X DSC-XRD DSC DSC-FTIR 6-10) DSC-XRD DSC-FTIR S pos S conf S or 2003 The Japan Society of Calorimetry and Thermal Analysis. 161

2 φ N 2π π 0 N(φ )sinφ dφ (5) cos 2 φ cos 2 φ π π 0 N(φ )cos 2 φ sinφ dφ 0 N(φ )sinφ dφ (6) Fig.1 The coordinate system defining the orientation of crystal and molecule in terms of the angles φ and ϕ. f φ f φ 3cos2 φ 1 2 (7) IR S or CCD XRD CCDXRDFTIR PFTIR DSC- CCDXRD DSC-PFTIR Fig.1 ON ON Z φ ON XY ϕ ϕ ON Z φ 11) Z O N N dφ dϕ dn dφ dϕ da N(φ, ϕ ) dn N(φ ϕ )da N(φ ϕ )sin φdφdϕ (2) (2) π 2π N N(φ ϕ )sinφdφdϕ (3) 0 0 N(φ, ϕ ) N 0 N 4π N 0 (4) ϕ φ φ Z f φ 1Z f φ 0.5 f φ 0 M Fig.1 X Y Z i j k M (sinφ sinϕ)i (sinφ cosϕ)j (cosφ)k (8) 12) (a co ) // (a co ) 12) (a co ) // K c cos 2 φ (9) (a co ) K c sin 2 φ cos 2 ϕ (10) K c cos 2 ϕ 1/2 (9) (a co ) K c (1 cos 2 φ)/2 (11) (9) (10) f φ (a co ) // K c (2f φ 1)/3 (12) (a co ) K c (1 f φ )/3 (13) (D co ) (a co ) /(a co ) // f φ f φ 1 Dco (14) 2D c o 1 162

3 DSC-XRDDSC-FTIR (b) (a) (b) DSC heat flow / µw (a) Fig.3 Two dimensional XRD profiles of (a) uniaxial drawn and (b) undrawn ipp. The insert arrow shows stretching direction. Fig.2 DSC heating curves of (a) uniaxial drawn ipp and (b) undrawn ipp. ipp General Science Corp., USA mm 50 mm 4.5 DSC DSC-200 ipp ipp 5 mg 5 min DSC-XRD CCD M06XCE XRD 50 kv 24 ma CuKα nm DSC 13) ipp 13) 5mg DSC min 1 XRD DSC-FTIR FTIR620 DSC MCT ipp 0.1 mm KBr 13) FTIR 2cm ipp 0 90 DSC min 1 DSC Fig.2 ipp Fig.2(a)160 ipp Fig.2(b) ippipp 136 J g J g 1 ipp J g 1 14) ipp 83 %ipp 87 % DSC 2 XRD Fig.3 Fig.3(a) ipp Fig.3(b) ipp ipp XRD Fig.2(a) ipp 15) ipp XRD Fig.2(b) ipp XRD XRD Fig.4 Fig.4(a) Fig.4(b) 163

4 Intensity 10 3 / c.p.s (a) (b) DSC heat flow / µw (b) (c) (a) Orientation function 2θ / deg Intensity 10 3 / c.p.s (c) (d) Fig.5 Temperature change of the crystallographic orientation function of the c-axis, f c (a) and the b-axis, f b (b) overlapped on DSC curve (c) for drawn ipp obtained by the simultaneous DSC- XRD at 2 min 1. Fig Fig.4(c) Fig.4(d) φ 90 ipp 00k c c c Fig.4(c)Fig.4(d) c 16) cos 2 φ c φ / deg One-dimensional XRD profiles (a) perpendicular and (b) parallel to the drawn direction and the azimuthal intensity profiles of the (c) (110) and (d) (130) planes obtained from twodimensional XRD profile shown in Fig.3(a). 1 (1 2sin2 θ 2)cos 2 φ 1 (1 2sin 2 θ 1)cos 2 φ 2 (15) sin 2 θ 1 sin 2 θ 2 cos 2 φ 1 cos 2 φ 2 (6) θ 1 θ b ipp 15) a nm b nm c nm β 99.3 θ 1 θ (15) c (7) c f c DSC Fig.5 DSC c f c(a) f c 0.6 c f c /2 0 b 040 (6) (7) b f b Fig.5 (b) f b b c c b b c Fig.5 f b(b) DSC b 0 c ipp DSC-FTIR IR Fig.6 IR IR Fig cm cm cm 1 5cm 1 164

5 DSC-XRDDSC-FTIR wave number / cm 1 DSC heat flow / µw Fig.7 Orientation function Temperature change of the orientation function of c-axis of helical conformation, f h overlapped with DSC curve for drawn ipp at 2 min 1. Fig.6 Three-dimensional polarized IR spectra of uniaxial drawn ipp obtained by the simultaneous DSC- FTIR measurement during heating at 2 min 1 shown in the wave number - temperature plane. The counter line shows the absorbance of spectra. IR spectra were measured by rotating the polarizer at 0 and 90 alternately every 50 sec. 840 cm 1 C-C CH cm 1 CH 3 17) ipp nm 18) 995 cm 1 c 995 cm 1 f h (14) DSC Fig.7 DSC 168 DSC 163 Fig.5DSC-XRD f h c f c Fig.5 FTIR f h c f c f h ipp f h DSC 163 DSC Fig.5 DSC Fig.7 ipp 0 ipp DSC-XRD 165

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