Abstract
The tensile modulus of elasticity and yield strength of semicrystalline random copolymers of propylene with different amount on ethylene or 1-butene co-units were analyzed as a function of the crystallinity and the crystal habit/shape. Samples were prepared by cooling the melt to ambient temperature, and subsequent annealing at elevated temperature. Variation of the cooling rate between 10−1 and 103 K s−1 and of the temperature of annealing allowed preparation of semicrystalline specimens with either lamellar or non-lamellar crystals of different size, and with different crystallinity between about 30 and 70%. Young’s modulus and yield strength increase with increasing crystallinity and consistently are lower for samples containing nodular, that is, almost isometric, non-lamellar crystals of low aspect ratio. For samples of identical crystallinity and crystal habit, an only minor effect of presence of co-units in the crystalline and amorphous phases is observed.
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References
Piccarolo S (1992) Morphological changes in isotactic polypropylene as a function of cooling rate. J Macromol Sci Phys B 31:501–511
Zia Q, Androsch R, Radusch HJ, Piccarolo S (2006) Morphology, reorganization, and stability of mesomorphic nanocrystals in isotactic polypropylene. Polymer 47:8163–8172
Binsbergen FL, De Lange BGM (1968) Morphology of polypropylene crystallized from the melt. Polymer 9:23–40
Bassett DC, Olley RH (1984) On the lamellar morphology of isotactic polypropylene spherulites. Polymer 25:935–943
Olley RH, Bassett DC (1989) On the development of polypropylene spherulites. Polymer 30:399–409
Gezovich DM, Geil PH (1968) Morphology of quenched polypropylene. Polym Eng Sci 8:202–207
Hsu CC, Geil PH, Miyaji H, Asai K (1986) Structure and properties of polypropylene crystallized from the glassy state. J Polym Sci Polym Phys 24:2379–2401
Ogawa T, Miyaji H, Asai K (1985) Nodular structure of polypropylene. J Phys Soc Jpn 54:3668–3670
De Santis F, Adamovsky S, Titomanlio G, Schick C (2006) Scanning nanocalorimetry at high cooling rate of isotactic polypropylene. Macromolecules 39:2562–2567
Gradys A, Sajkiewicz P, Minakov AA, Adamovsky S, Schick C, Hashimoto T, Saijo K (2005) Crystallization of polypropylene at various cooling rates. Mat Sci Eng A413–A414:442–446
Zannetti R, Celotti G, Fichera A, Francesconi R (1969) The structural effects of annealing time and temperature on the paracrystal–crystal transition in isotactic polypropylene. Makromol Chem 128:137–142
O’Kane WJ, Young RJ, Ryan AJ, Bras W, Derbyshire GE, Mant GR (1994) Simultaneous SAXS/WAXS and d.s.c. analysis of the melting and recrystallization behaviour of quenched polypropylene. Polymer 35:1352–1358
Wang ZG, Hsiao BS, Srinivas S, Brown GM, Tsou AH, Cheng SZD, Stein RS (2001) Phase transformation in quenched mesomorphic isotactic polypropylene. Polymer 42:7561–7566
Androsch R (2008) In situ atomic force microscopy of the mesomorphic–monoclinic phase transition in isotactic polypropylene. Macromolecules 41:533–535
Zia Q, Radusch HJ, Androsch R (2007) Direct analysis of annealing of nodular crystals in isotactic polypropylene by atomic force microscopy, and its correlation with calorimetric data. Polymer 48:3504–3511
Farrow G (1963) Crystallinity, ‘crystallite size’ and melting point of polypropylene. Polymer 4:191–197
Martorana A, Piccarolo S, Sapoundjieva D (1999) SAXS/WAXS study of the annealing process in quenched samples of iostactic poly(propylene). Macromol Chem Phys 200:531–540
Natale R, Russo R, Vittoria V (1992) Crystallinity of isotactic polypropylene films annealed from the quenched state. J Mater Sci 27:4350–4354
Zia Q, Androsch R, Radusch HJ (2010) Effect of the structure at the micrometer and nanometer scales on the light transmission of isotactic polypropylene. J Appl Polym Sci 117:1013–1020
Zia Q, Radusch HJ, Androsch R (2009) Deformation behavior of isotactic polypropylene crystallized via a mesophase. Polym Bull 63:755–771
De Rosa C, Auriemma F, Ruiz de Ballesteros O, Resconi L, Camurati I (2007) Crystallization behavior of isotactic propylene–ethylene and propylene–butene copolymers: effect of comonomers versus stereodefects on crystallization properties of isotactic polypropylene. Macromolecules 40:6600–6616
De Rosa C, Auriemma F, Ruiz de Ballesteros O, Resconi L, Camurati I (2007) Tailoring the physical properties of isotactic polypropylene through incorporation of comonomers and the precise control of stereo- and regioregularity by metallocene catalysts. Chem Mater 19:5122–5130
Hosier IL, Alamo RG, Lin JS (2004) Lamellar morphology of random metallocene propylene copolymers studied by atomic force microscopy. Polymer 45:3441–3455
Jeon K, Palza H, Quijada R, Alamo RG (2009) Effect of comonomer type on the crystallization kinetics and crystalline structure of random isotactic propylene 1-alkene copolymers. Polymer 50:832–844
Poon BC, Dias P, Ansems P, Chum SP, Hiltner A, Baer E (2007) Structure and deformation of an elastomeric propylene–ethylene copolymer. J Appl Polym Sci 104:489–499
Poon B, Rogunova M, Hiltner A, Baer E, Chum SP, Galeski A, Piorkowska E (2005) Structure and properties of homogeneous copolymers of propylene and 1-hexene. Macromolecules 38:1232–1243
Poon B, Rogunova M, Chum SP, Hiltner A, Baer E (2004) Classification of homogeneous copolymers of propylene and 1-octene based on comonomer content. J Polym Sci Polym Phys 42:4357–4370
Mileva D, Androsch R, Radusch HJ (2008) Effect of cooling rate on melt-crystallization of random propylene–ethylene and propylene-1-butene copolymers. Polym Bull 61:643–654
Mileva D, Zia Q, Androsch R, Radusch HJ, Piccarolo S (2009) Mesophase formation in poly(propylene-ran-1-butene) by rapid cooling. Polymer 50:5482–5489
Mileva D, Androsch R, Zhuravlev E, Schick C (2009) Critical rate of cooling for suppression of crystallization in random copolymers of propylene with ethylene and 1-butene. Thermochim Acta 492:67–72
Foresta T, Piccarolo S, Goldbeck-Wood G (2001) Competition between α and γ phases in isotactic polypropylene: effects of ethylene content and nucleating agents at different cooling rates. Polymer 42:1167–1176
Zia Q, Androsch R, Radusch HJ, Ingolič E (2008) Crystal morphology of rapidly cooled isotactic polypropylene: a comparative study by TEM and AFM. Polym Bull 60:791–798
Androsch R, Wunderlich B (2001) Heat of fusion of the local equilibrium of melting of isotactic polypropylene. Macromolecules 34:8384–8387
Androsch R, Wunderlich B (2001) Reversible crystallization and melting at the lateral surface of isotactic polypropylene crystals. Macromolecules 34:5950–5960
Brucato V, Piccarolo S, La Carrubba V (2002) An experimental methodology to study polymer crystallization under processing conditions. The influence of high cooling rates. Chem Eng Sci 57:4129–4143
Piccarolo S, Alessi S, Brucato V, Titomanlio G (1993) Crystallization behaviour at high cooling rates of two polypropylenes. In: Dosiere M (ed) Crystallization of polymers. Kluwer, Dordrecht, pp 475–480
Flory PJ (1954) Theory of crystallization in copolymers. Trans Faraday Soc 1:848–857
Sanchez IC, Eby RK (1975) Thermodynamics and crystallization of random copolymers. Macromolecules 8:638–641
Jeon K, Chiari YL, Alamo RG (2008) Maximum rate of crystallization and morphology of random propylene ethylene copolymers as a function of comonomer content up to 21 mol %. Macromolecules 41:95–108
Hoffmann JD, Davis GT, Lauritzen JI Jr (1976) The rate of crystallization of linear polymers with chain folding. In: Hannay HB (ed) Treatise on solid state chemistry, crystalline and noncrystalline solids, vol 3. Plenum Press, New York
Seitz JT (1993) The estimation of mechanical properties of polymers from molecular structure. J Appl Polym Sci 49:1331–1351
Rowe RC, Roberts RJ (1995) Interrelationships between the yield stress, tensile fracture strength and Young’s modulus of elasticity of films prepared from cellulose ethers and esters. J Mater Sci Lett 14:420–421
Halpin JC, Kardos JL (1972) Moduli of crystalline polymers employing composite theory. J Appl Phys 43:2234–2241
Kardos JL, Raisoni J (1975) The potential mechanical response of macromolecular systems—a composite analogy. Polym Eng Sci 15:183–190
Kardos JL, Piccarolo S, Halpin JC (1978) Strength of discontinuous reinforced composites: II. Isotropic crystalline polymers. Polym Eng Sci 18:505–511
Bédoui F, Diani J, Régnier G (2004) Micromechanical modeling of elastic properties in polyolefins. Polymer 45:2433–2442
Pukanszky B, Mudra I, Staniek P (1997) Relation of crystalline structure and mechanical properties of nucleated polypropylene. J Vinyl Addit Technol 3:53–57
Reuss A (1929) Berechnung der Fließgrenze von Mischkristallen auf Grund der Plastizitätsbedingung für Einkristalle. Z Angew Math Mech 9:49–58
Balta Calleja FJ, Fakirov S (2000) Microhardness of polymers. Cambridge University Press, Cambridge
Tranchida D, Bartczak Z, Bielinski D, Kiflie Z, Galeski A, Piccarolo S (2009) Linking structure and nanomechanical properties via instrumented nanoindentations on well-defined and fine-tuned morphology poly(ethylene). Polymer 50:1939–1947
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Financial support by the Deutsche Forschungsgemeinschaft (DFG) is greatly acknowledged.
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Mileva, D., Zia, Q. & Androsch, R. Tensile properties of random copolymers of propylene with ethylene and 1-butene: effect of crystallinity and crystal habit. Polym. Bull. 65, 623–634 (2010). https://doi.org/10.1007/s00289-010-0274-1
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DOI: https://doi.org/10.1007/s00289-010-0274-1