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

  • G. Ungar
  • E. G. R. Putra
  • D. S. M. de Silva
  • M. A. Shcherbina
  • A. J. Waddon
Chapter
First Online:
Part of the Advances in Polymer Science book series (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.

Polymer crystallization Nucleation Long alkanes Surface roughness Curved faces 

Abbreviations

A

Stem attachment rate

a0,b0

Unit cell parameters

AFM

Atomic force microscopy

B

Stem detachment rate

b

Width of a molecular chain

E

Extended chain form (= F1)

F2, F3, …, Fm

“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(a0/b0)

Δϕ

Bulk free energy of crystallization

G

Crystal growth rate

Δhf

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)

lSAXS

SAXS long period

LH theory

The theory of Lauritzen and Hoffman

m = L/l

Number of folds per chain +1

Mn

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

Tc

Crystallization temperature

TcFx-Fy

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

Td

Dissolution temperature

Tm

Melting temperature

TR

Roughening transition temperature

ΔT

Tm − Tc or Td − Tc = supercooling

v

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

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Copyright information

© Springer-Verlag Berlin Heidelberg  2005

Authors and Affiliations

  • G. Ungar
    • 1
  • E. G. R. Putra
    • 1
  • D. S. M. de Silva
    • 1
  • M. A. Shcherbina
    • 1
  • A. J. Waddon
    • 1
  1. 1.Department of Engineering MaterialsUniversity of SheffieldSheffield S1 3JDUK

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