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Changes in Melting Behaviour With Radial Distance From Spheruite

Changes in Melting Behaviour With Radial Distance From Spheruite

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Published by: Ehteshamul Islam on Jun 24, 2012
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Changes in the Melting Behavior with the Radial Distancein Isotactic Polypropylene Spherulites
 J. J. Thomson Physical Laboratory, University of Reading, Whiteknights, Reading RG6 6AF, United Kingdom
Borealis Polymers Oy, P.O. Box 330, FIN-06101 Porvoo, Finland
 Received 16 April 2003; revised 2 June 2003; accepted 3 June 2003
The melting of highly tactic
-polypropylene occurs in two stages even forcrystallization at 145 °C, a temperature at which reorganization during scanning isnegligible. A comparison of two such polypropylenes, one nucleated and the other notnucleated, together with fractions from the latter, has been made with electron micros-copy following permanganic etching, in addition to differential scanning calorimetry.This has allowed the two melting stages to be assigned to two components of thelamellar morphology, with progressive changes in both occurring with increasing radialdistance within a spherulite. The highest melting temperature is for dominant radiallamellae far from a spherulite center. The lowest melting regions are the evenlycrosshatched spherulite centers and a narrow peripheral band. Lower melting is at-tributed to the suppression of isothermal lamellar thickening paralleling recent directdemonstrations in polyethylene.
© 2003 Wiley Periodicals, Inc. J Polym Sci Part B: PolymPhys 41: 2342–2354, 2003
poly(propylene) (PP); spherulites; electron microscopy; melting point;crystallization
The properties of crystalline polymers such aspolyethylene (PE) and polypropylene (PP) dependon their crystallization and processing history inlarge measure via the effects on the constituentlamellae. The history of a given material mayconveniently be characterized by thermal analy-sis via the variation of the melting point with thelamellar thickness together with possible contribu-tions from defective or deformed lattices. In melt-crystallized polymers, the lamellar thickness de-pends not only on the crystallization temperature(supercooling) but also on the isothermal lamellarthickening after crystallization. Although inter-pretation along these lines is relatively straight-forward with PE, the
form of isotactic PP isaltogether more challenging. Here a major fea-ture is crosshatching, so that in PP, the earlystages of growth are based not on a single lamellabut on an object called a quadrite,
unique to PP,consisting of two equivalent twinned sets of la-mellae.Thiswasfirstseeninsolution-crystallizedPP, but it was soon thereafter observed in nucle-ated specimens of melt-crystallized bulk PP.
Inmelt-crystallized PP, the quadrite, as it growsoutward, develops into a system of radiating dom-inant lamellae that enclose subsidiary lamellaegenerated by crosshatching. The relief generatedby permanganic etching, which attacks the sub-sidiary lamellae more than the dominant ones,also increases with distance from the center.
In a previous article, the effect of nucleation onthe morphology and thermal behavior of a PP
Journal of Polymer Science: Part B: Polymer Physics, Vol. 41, 2342–2354 (2003) © 2003 Wiley Periodicals, Inc.
homopolymer was presented.
Thermal analysisrevealed the presence of two populations of lamel-lae with different melting temperatures, and atechnique of partial melting identified the realspace location of the two sets of lamellae, with theupper melting peak corresponding to the contin-uous radial dominant lamellae revealed in micro-graphs of etched specimens. In addition, thecrosshatched centers of the spherulites alsomelted at a temperature lower than the dominantradiating lamellae. The progressive developmentin the thermal properties with growth from thecenter was shown by comparison with a similarspecimen with added nucleant. In this, the spaceavailable for the development of each spherulitewas severely restricted, and during the middlestages of growth, which characterized the bulk of this specimen, the difference in the melting pointwas not so great, so it could be deduced that thedifferentiation of the two melting populationsshould occur progressively, from the center of thespherulite outward.The earlier investigation also shed light on thequestion of whether the development of doublemelting peaks was associated with molecularfractionation. In PE, sizeable fractions of lowermolecular weights
or greater short-chainbranching stay molten during the main crystalli-zation
and give a lower melting lamellar pop-ulation on cooling. However, the question wasstill open with respect to PP. Previously availablePP materials generally contained material of lower tacticity in lower molecular weight frac-tions.
However, the availability for the afore-mentioned work of a very highly tactic materialknown as high-crystallinity polypropylene (HCPP)showed that the behavior was intrinsic to PP, re-gardless of molecular defects.The previous work
only compared one nucle-ated specimen with its unnucleated counterpart. At the high crystallization temperature chosen(145 °C), the density of nuclei given by addedforeign nucleating agents is limited. In this work,the self-nucleation technique
allows the in- vestigation to be extended to much higher nucle-ation densities, particularly those at which theentire specimen is filled with a material charac-teristic of the very earliest stages of growth.Moreover, the conclusions drawn indirectly in theprevious work, that the radial morphological de- velopments are largely independent of molecularfractionation, are confirmed by their observationin a series of fractions of various narrowly distrib-utedmolecularweights.Thechangesinthemeltingpoint stem instead from morphologically relateddifferences in isothermal lamellar thickening.
The PPs used were a modern HCPP homopolymerfrom Borealis (HCPP1) studied in the previouswork,
along with fractions prepared from it, anda very similar polymer (HCPP2) that was nucle-ated with Borstar nucleation technology. Thefractionation was carried out according to the mo-lecular weight with ethylene glycol monobutylether/diethylene glycol monobutyl ether as a sol- vent/nonsolvent pair (see ref. 16 for details). Forcomparison, a somewhat older type of Ziegler–Natta polypropylene (ZNPP) was also used insome experiments. The characteristics of all thesematerials are given in Table 1.
Thermal Treatments
 All the specimens were prepared in a PerkinElmerDSC-2C. Some of these, of HCPP1 and HCPP2,
Table 1.
Properties of the PP Homopolymers and Their FractionsHCPP1 KN6 KN8 KN10 KN11 KN12 HCPP2 ZNPPMelt Flow Rate (2.16 kg g/10 min) 6.5 8.6 19 Xylene-soluble (wt %) 1.4 1.1 3.1mmmm 97.8 97.38 99.42 99.1 99.32 99.61 98.2 93.0Melting Temperature,
(°C) 165.8 163.8 165.3 166.3 166.6 167.6 167.2 164.3Crystallinity (%) 53.7 58.2 57.1 57.2 55.6 54.2 55.4 42.8Crystallization Temperature,
(°C) 121.9 118.5 119.5 119.6 120.8 122.2 129.4 109.4
(Da) 64,700 56,600 77,800 104,200 192,900 215,300 62,300 75,100
(Da) 305,000 120,000 170,000 219,000 416,000 478,000 293,000 208,000
4.7 2.1 2.2 2.1 2.2 2.2 4.7 2.8
were directly crystallized from the melt via melt-ing at 210 °C for 2 min and cooling at 80 K min
to the crystallization temperature of 145 °C, atwhich temperature they were held for a specifiedtime. Other specimens of HCPP1 with nucleationenhanced by self-seeding were prepared in twostages. In the first stage, they were melted at 210°C and cooled at 10 K min
to 50 °C. In thesecond, they were heated at 10 K min
up to thechosen seeding temperature and immediatelycooled at 80 K min
to 145 °C, at which temper-ature they were held for a chosen time. We canprecisely control the nucleation density, takingaccount of the relationship between the meltingcurve of the preliminary specimen and the chosenself-seeding temperatures, as explained in ref. 17. At the end of the isothermal crystallizationtime, the melting endotherms of some specimenswere obtained by immediate heating at a rate of 10 K min
. Other specimens were quenched bybeing removed as quickly as possible from thedifferential scanning calorimeter and placed on acold metal surface (immediately before this, thedifferential scanning calorimeter was set to cool-ing at a nominal rate of 320 K min
to avoid asudden input of heat as the sample head wasopened). Generally, half of each quenched speci-menwasusedforthermalanalysis,reheatedfrom50 °C at a rate of 10 K min
, and half wasreserved for microscopy.
Etching and Microscopy
Samples so prepared were etched for 0.5 h in apublished permanganic reagent:
a 1% (w/v) so-lution of potassium permanganate in an acid mix-ture consisting of 10 volumes of concentrated sul-furic acid, 4 volumes of orthophosphoric acid(minimum 85%; Merck, United Kingdom), and 1 volume of water. A standard two-stage procedure with celluloseacetate
yielded shadowed (Ta/W) carbon repli-cas for transmission electron microscopy (TEM)studies: the textures of these materials were toofine for useful information at the lamellar level toeasily be obtained by scanning electron micros-copy (SEM). The use of SEM was confined tolower magnifications to provide a wider texturalcontext.
To set the background for the work that follows,we show the effect of artificial nucleation on PP inthe SEM micrographs in Figure 1 (note that thespecimens were tilted at 45° for improved con-trast
). At 145 °C, the unnucleated HCPP1 formsspherulites that can be grown to a radius of about0.2mmbeforeimpingement.ThespecimeninFig-ure 1(a) was allowed to crystallize for 2 h, whenmost of the PP was still molten, before quenching.What is seen in the larger part of the specimen isa quenched matrix, most of which is small, finelytextured spherulites, but some is present as aring of finely textured material developed aroundthe high-temperature spherulites, which isknown as a quench halo. In comparison, HCPP2in Figure 1(b) is seen to have crystallized fullywell before 2 h, with spherulites typically lessthan 20
m in radius.
Thermal Analysis
The crystallization temperature of 145 °C waschosen because the crystals that formed show lit-
Figure 1.
SEM images of (a) HCPP1 and (b) HCPP2crystallizedat145°Cfor2h.Thespecimensweretilted45°.

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