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The Effect of Self-Poisoning on Crystal Morphology and Growth Rates

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Interphases and Mesophases in Polymer Crystallization I

Part of the book series: Advances in Polymer Science ((POLYMER,volume 180))

Abstract

Recent extensive experimental work and the limited theoretical studies of the phenomenon ofself-poisoning of the crystal growth face are reviewed. The effect arises from incorrect but nearlystable stem attachments which obstruct productive growth. Experimental data on the temperature andconcentration dependence of growth rates and the morphology of long-chain monodisperse n-alkanesfrom C162H326 to C390H782are surveyed and compared to some previously established data on poly(ethylene oxide) fractions, aswell as on polyethylene. The anomalous growth rate minima in both temperature and concentration dependenceof growth rates are accompanied by profound changes in crystal habits, which have been analysed interms of growth rates on different crystallographic faces, and in terms of separate rates of stepnucleation and propagation. In some cases non-nucleated rough-surface growth is approached. Thephenomena covered include “poisoning” minima induced by guest species, the “dilutionwave” effect, autocatalytic crystallization, pre-ordering in solution, two-dimensional nucleation,and the kinetic roughening and tilt of basal surfaces.

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Abbreviations

A :

Stem attachment rate

a 0,b 0 :

Unit cell parameters

AFM:

Atomic force microscopy

B :

Stem detachment rate

b :

Width of a molecular chain

E:

Extended chain form (= F1)

F2, F3, …, F m :

“Integer forms” with chains folded in two, three etc.

ΔF :

Overall free energy of crystallization

ϕ:

Chain tilt angle with respect to layer normal

φ:

Obtuse angle between (110) and (−110) planes in alkane and polyethylene crystals.φ/2 = tan−1(a 0/b 0)

Δϕ:

Bulk free energy of crystallization

G :

Crystal growth rate

Δh f :

Heat of fusion

i :

Rate of initiation (secondary nucleation) of a new row of stems on crystal growthface

IF:

Integer folded

K :

Slope of the linear dependence of G on ΔT

L :

Chain length

l :

Length of straight-chain segment traversing the crystal (stem length)

l SAXS :

SAXS long period

LH theory:

The theory of Lauritzen and Hoffman

m = L/l :

Number of folds per chain +1

M n :

Number average molecular mass

n :

Number of monomer repeat units per chain (e.g., number of carbons in an alkane); alsoreaction order

NIF:

Non-integer folded form

PE:

Polyethylene

PEO:

Poly(ethylene oxide)

q :

Modulus of the wavevector, q = 4π(sin θ)/λ,where θ is half the scattering angle and λ is radiation wavelength

SANS:

Small-angle neutron scattering

SAXS:

Small-angle X-ray scattering

σ:

Side-surface free energy

σe :

End- or fold-surface free energy

T c :

Crystallization temperature

T Fx-Fy c :

Growth transition temperature between two successive folded forms (e.g., T E-F2 c is the temperature of transition between extended (E) and once-folded (F2)chain growth)

T d :

Dissolution temperature

T m :

Melting temperature

T R :

Roughening transition temperature

ΔT :

T m − T c or T d − T c = supercooling

v :

Rate of step propagation on a crystal growth face (often also referred to as g)

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Authors and Affiliations

  1. Department of Engineering Materials, University of Sheffield, Sheffield S1 3JD, UK

    G. Ungar, E. G. R. Putra, D. S. M. de Silva, M. A. Shcherbina & A. J. Waddon

Authors
  1. G. Ungar
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  2. E. G. R. Putra
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  3. D. S. M. de Silva
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  4. M. A. Shcherbina
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  5. A. J. Waddon
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Correspondence to G. Ungar .

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Editors and Affiliations

  1. Dipartimento di Chimica Materiali e Ingegneria Chimica “Giulio Natta”, Politecnico di Milano, Via L. Mancinelli, 7, 20131, Milano, Italy

    Giuseppe Allegra

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Ungar, G., Putra, E.G.R., de Silva, D.S.M., Shcherbina, M.A., Waddon, A.J. (2005 ). The Effect of Self-Poisoning on Crystal Morphology and Growth Rates. In: Allegra, G. (eds) Interphases and Mesophases in Polymer Crystallization I. Advances in Polymer Science(), vol 180. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b107232

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