Vibrational Spectroscopic Study on the Origin of Stress Oscillation during Step-Wise Stretching in Poly(Ethylene Terephthalate)

Abstract

The origin of the phenomenon of stress oscillation during step-wise stretching at room temperature for amorphous poly(ethylene terephthalate) (PET) was investigated using vibrational spectroscopy. For the first time, transmission Fourier transform infrared (FT-IR), attenuated total reflection (ATR) FT-IR, and micro-Raman spectroscopies were used in order to investigate the correlation of the orientation of the molecular chains, their conformational transformations, and the appearance of stress-induced crystallization to the phenomenon of stress oscillation during the step-wise stretching procedure. The phenomenon of stress oscillation occurs when amorphous PET is exposed to mechanical stress during which the extension rate is increased in a step-wise manner. This phenomenon leads to the formation of a pattern of opaque and transparent stripes (“striated” or oscillating region), clearly distinguished from the unstretched (“bulk”) and the “necking” regions. Both infrared and Raman spectroscopic investigations revealed that the main conformational transformations and a significant increase of the crystallinity occur simultaneously in the “striated” region. Polarized infrared experiments showed the presence of increased molecular orientation, which is more profound for the “intense striated” region. Finally, micro-Raman spectroscopy allowed the study of opaque and transparent stripes individually and showed that the opaque stripes are more crystalline. Thus, our findings provide conclusive experimental support for the theory, which directly correlates the appearance of the stress-oscillation phenomenon with the induction of crystallinity and heat release and is based on Barenblatt's model. Our study also provides new conformational assignments for the infrared bands in PET for the high-frequency region from 3200 to 3800 cm⁻¹. Specifically, the bands at 3336 cm⁻¹ and at 3298 cm⁻¹ have been attributed to the trans and gauche conformations, respectively.

Keywords

Poly(ethylene terephthalate)PET Stress oscillation Crystallinity

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References

Ward

I. M.

, Structure and Properties of Oriented Polymers (Chapman and Hall, London, 1997), 2nd ed.

Štokr

Schneider

Doskočilová

Lövy

and Sedláček

, Polymer 23, 714 (1982).

Rodríguez-Cabello

J. C.

Quintanilla

and Pastor

J. M

, J. Raman Spectrosc. 25, 335 (1994).

X. F.

and Hay

J. N

, Polymer 42, 8055 (2001).

Miyake

, J. Polym. Sci. 38, 479 (1959).

Manley

T. R.

and Williams

D. A

, Polymer 10, 339 (1969).

Ward

I. M.

and Wilding

M. A

, Polymer 18, 327 (1977).

Daubeny

Bunn

C. W.

and Brown

C. J

, Proc. R. Soc. London, Ser. A 226, 531 (1954).

Lin

S.-B.

and Koenig

J. L

, J. Polym. Sci., Polym. Phys. Ed. 20, 2277 (1982).

10.

Adar

and Noether

, Polymer 26, 1935 (1985).

11.

Dargent

Grenet

and Auvray

, J. Therm. Anal. 41, 1409 (1994).

12.

Ajji

Guévremont

Cole

K. C.

and Dumoulin

M. M

, Polymer 37, 3707 (1996).

13.

D'Esposito

and Koenig

J. L

, J. Polym. Sci., Polym. Phys. Ed. 14, 1731 (1976).

14.

Cole

K. C.

Ajji

and Pellerin

, Macromolecules 35, 770 (2002).

15.

Williams

A. D.

and Flory

P. J

, J. Polym. Sci., Part A-2 5, 417 (1967).

16.

Melveger

, J. Polym. Sci., Part A-2 10, 317 (1972).

17.

Cole

K. C.

Ajji

and Pellerin

, Macromol. Symp. 184, 1 (2002).

18.

Müller

F. H.

and Engelter

, Kolloidzeitschrift 150, 156 (1957).

19.

Barenblatt

G. I.

, Mech. Solids 5, 110 (1970).

20.

Andrianova

G. P.

Kechekyan

A. S.

and Kargin

V. A

, J. Polym. Sci., Part A-2 9, 1919 (1971).

21.

Roseen

, J. Mater. Sci. 9, 929 (1974).

22.

Mouzakis

D. E.

and Karger-Kocsis

, J. Appl. Polym. Sci. 68, 561 (1998).

23.

Karger-Kocsis

and Varga

, J. Appl. Polym. Sci. 62, 291 (1996).

24.

Ebener

Pleuger

and Petermann

, J. Appl. Polym. Sci. 71, 813 (1999).

25.

Godovsky

Y. K.

, Thermophysical Properties of Polymers (Springer, Berlin, 1992), pp. 221–225.

26.

Boyce

M. C.

and Haward

R. N

, The Physics of Glassy Polymers, Haward

R. N.

and Young

R. J

, Eds. (Chapman and Hall, London, 1997), 2nd ed., p. 251.

27.

Pleuger

Ph.D. Thesis “Mechanische Instabilitäten beim Kaltverstrecken thermoplastischer Polymere”, Shaker Verlag, Aachen, Germany (2001).

28.

Pakula

and Fischer

E. W

, J. Polym. Sci., Polym. Phys. Ed. 19, 1705 (1981).

29.

Gent

A. N.

and Madam

, J. Polym. Sci. Part B: Polym. Phys. 27, 1529 (1989).

30.

Karger-Kocsis

, in Handbook of Thermoplastic Polyesters, Fakiror

Ed. (Wiley-VCH, Weinheim, 2002), Chap. 16, p. 717.

31.

Karger-Kocsis

Benevolenski

O. I.

and Moskala

E. J

, J. Mater. Sci. 36, 3365 (2001).

32.

Toda

, Polymer 35, 36 (1994).

33.

Cunningham

Ward

I. M.

Willis

H. A.

and Zichy

, Polymer 15, 749 (1974).

34.

Yazdanian

Ward

I. M.

and Brody

, Polymer 26, 1779 (1985).

35.

Padibjo

S. R.

and Ward

I. M

, Polymer 24, 1103 (1983).

36.

Ward

I. M.

, Adv. Polym. Sci. 66, 81 (1985).

37.

Spiby

O' Neill

M. A.

Duckett

R. A.

and Ward

I. M

, Polymer 21, 4479 (1992).

38.

Guévremont

Ajji

Cole

K. C.

and Dumounlin

M. M

, Polymer 36, 3385 (1995).

39.

Ajji

Cole

K. C.

Dumoulin

M. M.

and Brisson

, Polymer 36, 4023 (1995).

40.

Lapersonne

Bower

D. I.

and Ward

I. M

, Polymer 33, 1277 (1992).

41.

Zhang

Ajji

and Jean-Marie

, Polymer 42, 8179 (2001).

42.

Duchesne

Kong

Brisson

Pézolet

and Prud'homme

R. E

, Macromolecules 35, 8768 (2002).

43.

Pellerin

Prud'homme

R. E.

Pézolet

Weinstock

and Griffiths

P. R

, Macromolecules 36, 4838 (2003).

44.

Pearce

Cole

K. C.

Ajji

and Dumoulin

M. M

, Polym. Eng. Sci. 37, 1795 (1997).

45.

Atkinson

J. R.

Biddlestone

and Hay

J. N

, Polymer 41, 6965 (2000).

46.

Walls

, Appl. Spectrosc. 45, 1193 (1991).

47.

Boerio

F. J.

Bahl

S. K.

and McGraw

G. E

, J. Polym. Sci., Polym. Phys. Ed. 14, 1029 (1976).

48.

Kitano

Kinoshita

and Ashida

, Polymer 36, 1947 (1995).

49.

Cobbs

W. H.

Jr. , and Burton

R. L.

, J. Polym. Sci. 10, 275 (1953).

50.

Hannon

M. J.

and Koenig

J. L

, J. Polym. Sci., Part A-2 7, 1085 (1969).

51.

Aharoni

S. M.

Sharma

R. K.

Szobota

J. S.

and Vernick

D. A

, J. Appl. Polym. Sci. 28, 2177 (1983).

52.

Radhakrishnan

and Kaito

, Polymer 42, 3859 (2001).

53.

Ito

Perreira

J. R. C.

Hsu

S. L.

and Porter

R. S

, J. Polym. Sci., Polym. Phys. 21, 389 (1983).

54.

Miller

R. G.

and Willis

H. A

, J. Polym. Sci. 19, 485 (1956).

55.

Aref-Azar

and Hay

J. N

, Polymer 23, 1129 (1982).

56.

Faisant de Champchesnel

J. B.

Bower

D. I.

Ward

I. M.

Tassin

J. F.

and Lorentz

, Polymer 34, 3763 (1993).

57.

Pellerin

Rouseau

M.-E.

Prud'homme

and Pézolet

, Appl. Spectrosc. 56, 17 (2002).

58.

Krim

, Adv. Polym. Sci. 2, 51 (1960).

59.

Mirabella

F. M.

Jr. , Appl. Spectrosc. 42, 1258 (1988).

60.

Koenig

J. L.

and Hannon

M. J

, J. Macromol. Sci., Part B 1, 119 (1967).

61.

Schmidt

P. G.

, J. Polym. Sci., Part A: Polym. Chem. 1, 1271 (1963).

62.

Yang

and Michielsen

, Macromolecules 35, 10108 (2002).

63.

Everall

Tayler

Chalmers

J. M.

MacKerron

Ferwerda

and Van der Maas

J. H

, Polymer 35, 3184 (1994).

64.

Bahl

S. K.

Cornell

D. D.

and Boerio

F. J

, J. Polym. Sci., Polym. Lett. Ed. 12, 13 (1974).

65.

Kazarian

S. G.

Branltey

N. H.

and Eckert

C. A

, Vib. Spectrosc. 19, 277 (1999).

66.

Yang

Long

Shen

and Qian

, Polym. Commun. 32, 125 (1991).

67.

Ellis

Roman

Marco

Gomez

M. A.

and Fatou

J. G

, Spectrochim. Acta, Part A 51, 2139 (1995).

68.

Derault

Gall

M. J.

Hendra

P. J.

Ellis

Cudby

M. E. A.

and Willis

H. A

, Proc. 2nd Eur. Symp. Polym. Spectrosc. 85 (1975).

69.

Bulkin

B. J.

Lewin

and DeBlase

F. J

, Macromolecules 18, 2587 (1985).

70.

Pastor

J. M.

Gonzalez

and De Saja

J. A

, J. Appl. Polym. Sci. 38, 2283 (1989).

71.

Kim

J. S.

Lewin

and Bulkin

B. J

, J. Polym. Sci., Part B: Polym. Phys. 24, 1783 (1986).

72.

Soto

and Voyiatzis

G. A

, Macromolecules 35, 2095 (2002).

73.

Rueda

D. R.

and Varkalis

, J. Polym. Sci., Polym. Phys. Ed. 33, 2263 (1995).

74.

Mehta

Baur

and Wunderlich

, J. Polym. Sci., Polym. Phys. Ed. 16, 289 (1978).

75.

Farrow

and Ward

I. M

, Polymer 1, 330 (1960).

76.

Busing

W. R.

Jin

Affholter

K. A.

and Wunderlich

, Macromol. Chem. Phys. 195, 803 (1994).

77.

Sharma

Desai

and Abhiraman

A. S

, J. Appl. Polym. Sci. 65, 2603 (1997).

78.

Dargent

Grenet

and Dahoun

, J. Polym. Eng. Sci. 37, 1853 (1997).

79.

Gupta

V. B.

Jain

A. K.

Radhakrishnan

and Chidambareswaran

P. K

, J. Macromol. Sci., Part B 33, 185 (1994).

80.

Kawakami

Ran

Burger

Sics

Chu

and Hsiao

B. S

, Macromolecules 36, 9275 (2003).