IGR – Microscale Polymer Processing
Note This report, although it accompanies the IGR form for the University of Leeds (the lead institution), is written to
cover both the contribution of Leeds and the achievements of entire MuPP project. This reflects the rational for a single
case for support in 1999, since the collaboration stood or fell by its close way of integrated working. It should therefore
be read alongside the forms for both this grant and for: GR/M60392 - Dr. M. R. Mackley, Cambridge University;
GR/M60385 - Dr. C. P. Buckley, Oxford University; GR/M60408 - Prof. R. W. Richards, Durham University;
GR/M60415 - Prof. A. J. Ryan, Sheffield University; GR/M59730 - Prof. P. D. Coates, Bradford University
Background
In 1999 a group of six industrial users of science and technology in polymer processing encouraged a consortium of six
UK University research groups in the science of polymer processing to work together in a new way [1]. The idea was a
co-ordinated approach to understanding and predicting the effects of molecular variables in polymer processing and
products (or “PPP modelling”) by experiments on model materials and a parallel multiscale modelling. The
motivation sprung from:

A range of new polymerisation techniques across several chemistries of polymer that afforded much greater control
of microstructure, molecular weight distribution and branching than before, opening op opportunities for molecular
engineering of a new generation of polymeric materials at the nanoscale [2-4].

A perception that the exploitation of these potentials would require a close and coordinated collaboration with the
latest polymer science under development at the universities.

An analysis that put UK science and engineering potentially in the forefront of world research in this area, able to
achieve a quantitative level of PPP modelling before rival projects in the USA and Japan.
At the same time, the EPSRC conceived of the MaPEA initiative, which became the ideal vehicle for the consortium,
funding the first 3 years of the project as “Microscale Polymer Processing” from 2000-2003. The project embedded
several fresh methodologies (see box):
DSM
BP
WELL-DEFINED MATERIALS
MODEL CALCULATIONS
(i) synthesis
(i) synthesis
(ii) rheology
(ii) rheology
Lucite
(iii) Scattering probes
(iv) process
(iv) process
(v) product
(v) product
Dow
BASF

Du Pont
The use of laboratory scale monodisperse and controlled architecture polymers to develop and hard-test
molecular theory and process modelling before it is then applied to more polydisperse industrial materials. By
scaling up the amounts sythesised of these materials, and scaling down at the level of process engineering,
monodisperse polymers became, in this “core” programme, for the first time the objects of process studies.
1

The management of these materials through a network of “strands” ( numbered (i)-(v) in the diagram)composed of
key UK groups from synthesis (I: Sheffield, Durham), rheological characterisation (II: Leeds), molecular process
scattering probes (III: Durham, Sheffield) complex flow measurements (IV: Cambridge, Bradford) and solid state
testing (V: Oxford, Leeds).

The parallel creation of a network of theoretical models by the Leeds group, working directly with molecular
variables at each strand level, and checked against results on the experimental materials.

Checking the developing models not only against rheological results, but also directly against X-ray (SAXS and
WAXS) and neutron (SANS) measurements at the molecular level of the scaled-down process flows.

The continual knowledge transfer into industrial application from day one via the “Satellite Project” concept.
Materials supplied by the industrial partnership became the focus for application studies of all or part of the
modelling and measurement “tree”, feeding back questions and targets into the generic “core” programme.

The long-term goal of supplying to industry a molecular-based methodology for the design of new processes and
products. We recognised that the first step in doing this was to demonstrate the science and technology on a model
material, laboratory scale.
Key Advances and Supporting Methodology
All of these general objectives have been met by the project, as well as the original ones specified on the IGR form. But
most important, the EPSRC grant has enabled the key UK groups in this field of materials science and engineering to
work together in a new way. Sharing the same set of materials, working towards the same multidisciplinary goals and
exchanging information both through consortium meetings and an active website has put UK molecular polymer
processing on a unique footing. We can summarise the impact of the PP project on the international state of the field
by contrasting the lack of key capabilities in 1999 to those now supplied by the project in 2003:
1999
 There was no visualisation of exact
MW/LCB processing
 There was no quantitative molecular
model of linear polymers in flow
 There were only preliminary ideas of how
to model LCB polymer melts.

Two groups providing visualisation of exact
MW/LCB processing.

Detailed and simple (ROLIEPOLY) quantitative
molecular models of linear polymers in flow.

Molecularly-derived models, and a general toolkit
for LCB polymers (multi-mode POM-POM)

There are both models and a large data-base of
experiments on exact MW/LCB relating process to
properties and morphologies.

flowSolve now works with all PP molecular
constitutive equations and transient flows with
GUI input and flowDis data-mining tools.

SANS and SAXS now probe polymer
conformation in process flows with theory.

A range of algorithms as well as “rules of thumb”
now stand on established ground, and are in the
hands of PP industrial teams.
 There were no models/experiments on
exact MW/LCB relating process to
properties.
 There were no flow solvers that worked
with molecular constitutive equations and
transient flows
 There were no direct experiments probing
polymer conformation in process flows.
 There were no algorithms for connecting
polymer architecture to processing
properties.
2003
The initial phase of the project naturally concentrated on building up the capabilities of the strands, or platforms,
themselves. This required considerable progress in all of them: new scaled-up model synthesis, extensional rheology,
new (especially more quantitative) theoretical models, novel scattering methods and experiments (especially on flowing
systems) and new ways of producing, testing and analysing small solid samples. In the second phase of the project
more emphasis was given to “cradle-to grave” project streams that cut across the strands – the central motivation for the
size and structure of the project itself.
2
First we summarise key advances, deliverables and results by strand, then do the same for the advances that depend on
cross-strand interdisciplinary working. References [Px] refer to the list of published papers and papers in preparation in
the annex, references [Pry] to the list of presentations. It is worth pointing out that the emergent results from connecting
the strands emerged predominantly as planned in the final half of the project, so constitute more of the “publications in
press and in preparation” of the annexes, although they have been well-presented at international conferences.
Strand I: Syntheis, Scale-up and Characterisation

The ability to synthesise narrow MWD linear architecture of PE and PS in up to 50g quantities, the latter in both
hydrogenous and deuterated versions. Monodisperse polybutadiene (PI<1.1) materials were supplied by the
Sheffield team at molecular weights of 10k, 22k, 50k, 112k, 250k, 500k . Monodisperse PS was supplied by the
Durham team at molecular weights of 68k, 236k, 258k, and 501k and perdeuterated PS at 100k, 240k, 450k and
1000k in quantities of up to 200g. The method is summarised in
sec-Bu-Li+ +
Li+
the box ([P1], [P25], [P28], [P30]).
-

n
1,4-polybutadiene (cis- and trans-)
A reliable diimine route of hydrogenating the dominant 1:4 PB
materials in solution to make <50g quantities of controlled
molecular weight polyethylene (with effectively 7% comonomer
side chains) ([P1], [P28], [Pr45]). A ruthenium route was also
investigated but developed in other ways ([P43]).
93%
m
1,2-polybutadiene
7%

A method of synthesising monodisperse PBD and PE combs in
10g quantities and a range of four such materials. The materials possess monodisperse backbone and arm
molecular weights, and a Poisson distribution of arm number ([P1], [P8], [P31]). The pendant vinyl groups of the
PB become, after chlorosilation, attachment points for the arms.

A selection of carefully blended materials of bimodal linear and linear/comb melts.
The table details the architectures of the model combs successfully synthesised, hydrogenated, and supplied to the
collaboration in both forms.
Short Code
Backbone mass
g/mol
Arm mass
g/mol
No. of
arms
Polydispersity
PBCn6
60,500
28,800
9.0
1.14
PBCn10
53,800
14,800
8.0
1.02
PBCn11
62,700
5,800
8.2
1.05
PBCn12
105,100
6,100
8.4
1.01
Strand II Advanced Rheology and Molecular Theory

A quantitative tube-theory, following the Doi-Edwards approach [5] for the
linear rheology and NSE measurements on linear polymers that incorporates for
the first time all the processes of reptation, contour length fluctuation, tension
equilibration and constraint release, agreeing quantitatively with data on PB and
PS project and literature data (see data comparison with G*() for a range of
monodisperse PS samples in figure) ([P14], [P15])

A quantitative theory for non-linear response of linear polymers incorporating
all the above plus stretch and convective constraint release (CCR), able to
predict rheology and scattering in strongly non-linear flows ([P5], [P6], [P21],
[P30], [P17])

A quantitative family of constitutive equations for (i) linear (the ROLIEPOLY equation [P13]) and (ii) branched
melts (the POMPOM equation [P9], [P19]) that incorporate segment stretch and constraint-release effects, yet are
suitable for flow-field computation. They have mathematical structures new to the field of constitutive equations.
The ROLIEPOLY equation is: where Ge and τd are the

3Ge 

21 
amplitude and time of a mode, κ is the flow gradient
tr  

1
3Ge

T
  



  IGe 








IG

e
tensor, α the CCR parameter and τr a Rouse (stretching)

d
r
tr



time.
3

An ab initio calculation for highly branched polymers of exact tree [P7], metallocene-catalysed [P4] and comb
[P31] melts that predicts extensional rheology, and a design tool to create tailored rheology from trimodal blends of
linear polymers (Industrial Satellite Project).

An first theory for the wide applicability, and limitations of ,the approximation of tube dilation to constraint-release
in star polymers ([P18]).

Sample-preparation and experimental methods for reliable linear and nonlinear transient shear and extensional
rheology of the project PS samples, and identification of high slip in PB materials in shear ([P8],[P10],
[P11],[P30],[P31], [P32]).

Experimental verification that the “damping function” of linear polymer melts is sensitive to the rate of imposition
of the initial step strain, due to CCR ([P41]).
Strand III Direct Molecular Probes of Structure in Flow

The development of a recirculating cell for SANS
measurements in a process flow of deuterated model
polymer and its successful mapping of the SANS-field in
deuterated linear polymers and blends ([P22], [P30], [P40]).
First paper accepted in the journal SCIENCE.

The measurement of single chain SANS structure factors as
a function of position in a complex flow field, and
comparison with molecular theory ([P30], [P40]) (see box
opposite).

The comparison of SANS and birefringence under the same
recirculating complex flow field ([P30], [P40]) via the
construction of two identical recirculating flow devices.

Systematic observations of structure development of semi-crystalline polymers (e.g. iPP, PE, PET, Nylon) using an
in-situ commercial extrusion device with SAXS/WAXS ([P23], [P25], [P27]) and the identification of strong preordering effects in iPP, but not in PE.

The design and implementation of new SAXS/WAXS detector technology that allows equal sensitivity in both qranges of the device. This is essential to the key objective of ascertaining whether pre-nucleation structuring in
crystallising melts is a real phenomenon or an observational artefact.

Construction of a Couette cell for in situ X-ray measurements and its implementation at Daresbury and the ESRF
([P25], [Pr39])

Isothermal crystallisation of branched, linear and blends as well as
commercial polymers to investigate early pre-nucleation stages of
structure development incorporating ‘spinodal decomposition’ like
kinetics, using simultaneous SAXS/WAXS. The identification of the
role of comb additives as strong only under shear ([Pr40],[P28]) (see
figure).

Screening of wide family of controlled architecture blends under
shear conditions using in-situ flat plate and Couette geometeries
obtaining SAXS/WAXS for structure development.
Strand IV Measurement and Modelling of Small-scale Process Flows

The ability to probe complex flows of as little as 7g of monodisperse material
in flow and stress fields in the (Mk4) Cambridge Multipass Rheometer
([Pr34], [P2],[P11], [P30], [P31], [Pr29]) (see figure for stress field around a
linear polymer flowing through a constriction) . Two opposing pistons force
the material under investigation reversibly though a replaceable test section.

The discovery that constriction outflow detail in the stress field is a very
sensitive measure of molecular architecture ([P2], [P31]).

The construction and implementation of a complementary recirculating
4
device in Bradford for flow measurements on small quantities ([Pr9], [Pr10], [P30]). The challenges of drawn-in
air, the driving system, minimising degradation, were all solved satisfactorily. This system became the core
technology of the Durham SANS flow cell (see strand III).

The development of laser sheet-lighting and birefringence technique for full stress and velocity field determination
in process flows ([Pr16], [Pr20], [Pr21])

The development of a Lagrangian flow solver, flowSolve, compatible with the materials (strand I) molecular
constitutive equations (strand II) and process geometries (strand IV) of the project. It now includes, GUI input files
and data-mining tools, capability of handling free-surface, time-dependent and non-isothermal flows (see figure for
a prediction of streamline and stress (colour-coded) for a branched polymer
flowing though a constriction) ([P2],[P30], [P31], [P32], [P44]).

The ability to process (extrusion of tape) with as little as 7g of polymer while
monitoring flow and stress fields. This was achieved by designing and making a
new insert for the Cambridge MPR that used antiparallel motion of the two
pistons to force the test material through a die on the side of the test piece, while
still keeping the ability to monitor the interior flow stress ([Pr30],[P36], [Pr33]).

A detailed description of the instabilities that ensue at moderate flow rates when
very monodisperse polymers are employed in a contraction flow ([P42]).
Strand V Solid State Properties



Ability to mould and compression test sub-gram samples of polystyrene
produced by the synthesis strands of the project. This from of test was
extensively used on model samples of limited amount ([Pr26], [Pr27]).
Ability to model constitutively elastic-viscoelastic deformation in glassy
polystyrene with pronounced strain-softening (see example graph). The solid
state model includes information from the rheological relaxation spectrum,
and the degree of frozen-in orientation ([Pr25],[Pr27]).
C
o
m
p
r
e
s
s
i
v
e
T
r
u
e
S
t
r
e
s
s
(
M
P
a
)
1
0
0
8
0
6
0
4
0
o
T
=
4
0
C
6
0
2
0
Discovery of apparently enhanced molecular weight effect in plastic
deformation of polystyrene with controlled thermal history, including a
dependence of the compressive yield stress on Mn, via the shift in Tg.
0
0
.0
0
.1
0
.2
0
.3
C
o
m
p
r
e
s
s
i
v
e
T
r
u
e
S
t
r
a
i
n

Development, construction and implementation of a haul-off device to solidify
tape products from the MPR in a controlled way. Measurement and correlation of yield stress and strain-hardening
on these samples.

Ability to do tensile and 3-point bend tests on MPR-extruded mini products, and on small compression-moulded
samples to explore the environmental stress cracking behaviour of the model materials ([P38], [Pr28]).

The discovery of regular crazing patterns in notch testing of monodisperse PS materials that have changed the
accepted picture of the PS craze energy ([Pr28],[P33],[P34]).

The discovery of a cold-rolling process for PS that results in a permanent toughening of the polymer ([P35]).
Emergent, Cross-Strand Capabilities
These results, that build on the interdisciplinary working of the consortium, constitute the key added-value of working
together as the PP consortium.

A managed transfer of monodisperse materials and information from synthesis in Durham or Sheffield, rheological
characterisation in Leeds, flow-visualisation and product extrusion in Cambridge or Bradford and solid state
measurements in Oxford or Leeds. In parallel a molecular model of all stages in this process and a set of software
tools (FlowSolve and FlowDis implemented across the consortium). The figure below shows tape extrusion
birefringence inside (c) and outside the flow cell (d) together with the FlowSolve calculation (b) based on
quantitatively modelled rheology (a), informed directly by chemical structure. This working methodology is a
world-first.
5
(a)
(b)
(c)
(d)

Knowledge-transfer of emerging capabilities to a series of “Satellite Project” applications within the collaborating
industrial partners. Several of these have led, or will lead to joint publication with industrial scientists. Examples
include: mathematical modelling of a BASF melt, experimental and theoretical study of die-swell phenomena of
new BP materials ([P44]), modelling tool for acrylic blends from INEOS, modelling software for branched
metallocene melts for Dow ([P4]) and a study of cross-linking PET for DuPont. Several partners have now
embodied the project software into their in-house analysis and prediction systems.

For the first time, a complex flow-field of tailored,
monodisperse melts has been modelled from
molecular structure upwards, and probed by both
neutron-scattering and stress-birefringence (see
figure, which shows the predicted and observed
scattering contour plots on the left of the
experimental slot-die, with stress patterns similarly
on the right). This central cross-strand
achievement could only have been done within a
collaboration such as PP. It has enabled us to
identify a range of different lengthscales and
timescales on which orientation in a melt may
vary, and explains from the advanced models of
the three key molecular processes in melts why
samples “isotropic” as far as birefringence can tell
may exhibit very anisotropic solid state properties
(especially fracture and strain-hardening) and
crystallisation kinetics, so crosses strands I-V in
their entirety. This work is currently under review
for publication in Science, and has been presented to considerable international acclaim ([P30], [P39], [Pr23]).

Combination of the molecular theory, flowSolve computation, synthesis and the MPR flow-cell have enabled the
project to predict for the first time a flow-scale process phenomenon in melts from first principles, then to observe
and characterise it. This is the special outflow “fang” pattern of frozen-in stresses that arise in the transient flow
when long chain branched polymers are forced through a constriction ([P2],[P31]). First observed in the MPR in
the case of LDPE, it has been identified as arising from the slow stretch modes of LCB polymers generally, and
arises in the projects own model comb materials.

The use of monodisperse and controlled-architecture polymers in a process environment for the first time has led to
clarity of effect, and consequently of insight, similar to those arising from their examination in simple rheology.
For example, in the case of monodisperse linear polymers, the flow rates leading to orientation and stretch
separate, as do the flow phenomena arising from them ([P11], [P30]). In the case of comb polymers, the effects of
changing branch length, backbone length and branch density can be individually seen ([P31],[Pr23],[Pr47])

Rapid feedback along the process hierarchy to advance the development of modelling capacity. Examples are
incorporation of reversing-flow effects at the molecular level in constitutive models [P2] and the developing
models for flow-induced crystallinity ([P24], [P27). The emergence of molecular quantitative descriptions of the
non-linear dynamics of the comb materials, combined with the awareness of the length-scale dependence of
orientation from the SANS programme, sheds light on the remarkable factors of 100 or more by which comb
additives at just a few percent accelerate crystallisation in a dominantly linear melt.

A focussed study of the two variables of, (i) Long Chain Branching (LCB) up to comb-like architectures ([P1][P8-P10],[P12], [P17-P19],[P31]), and (ii) Molecular Weight Distribution (MWC) up to trimodal blends
([P5,P6],[P11], [P13-P15], [P21], [P32], [P40]). From this extensive work has emerged both detailed theories and
tools for multiscale modelling of these materials, but also guidelines for resin-design. For example, LCB can be
6
tailored now at the molecular level to deliver strain-hardening at a targeted strain rate. Similarly in the solid state,
the polydispersity of a linear blend, and its process history can be controlled to target yield stress [Pr28].

The first experimental studies of crystallisation in semi-crystalline controlled-architecture polymers, in both
quiescent and flow-induced states ([P24], [P27), together with theoretical modelling, has identified new routes for
crystallisation kinetics in some materials.

The identification that some solid state properties correlate with anisotropy at the bond level (as measured by
birefringence), others more strongly with the independent degree of correlation at the chain level (as measured by
SANS). Examples of the first tend to be the (near) linear properties of modulus and yield stress, of the second the
highly non-linear properties of strain hardening or fracture stress. When coupled with the molecular/process
modelling tools of the project, the way is open to process design that deliberately creates tailored levels of bond and
chain anisotropy ([Pr27], [P33]).

The PP website (developed by Dr. T. Nicholson) has been a rich and vital working tool for the project, as well as
a public window on the scientific achievements. The password-controlled pages contain all chemical, rheological
and flow data for the project materials, permanent records of material presented as posters and orally at project
meetings, and is updated regularly. Project soft ware and user manuals may be downloaded from a doubly-secure
page. The public face of the website contains recent highlights of the project, and also the 6-monthly newsletters.
These are also mailed to a growing list of subscribers, mainly in industry. The website may be found at
http://irc.leeds.ac.uk/mupp.
Project Plan Review
The project plan differed only slightly from the envisaged one. This is especially remarkable for such a large and
interconnected project. Some of the eventual courses of the work were planned as options from the start. For example,
the hydrogenation route in solution developed in Sheffield was applied to the project PB materials rather than the
ruthenium-catalysed route investigated at Leeds. But making sure that material supply comes from at least two sources
for a complex project such as this is necessary to avoid “single point failures”.
The main change was the decision to restrict the solid-state work within the first 3-year term of the collaboration to the
amorphous PS materials, rather than to perform a superficial study of the semi-crystalline materials. This was due to (a)
the late availability of sufficient quantities of the hPB linear and comb materials and their blends, (b) the challenges
these materials presented for the melt-state processing on its own, and (c) the need for more work that envisaged to
develop the solid state testing on the simpler, PS samples.
Extensional measurements on the comb materials proved much harder than originally thought, but new ways of sample
preparation and recovery, and theory-assisted targeting of viable flow rates has overcome the problems to a large extent.
Similarly, the effects of compressibility of the melts, usually ignored, have been shown to modify strongly the pressure
transients in the MPR device on startup flow. While not affecting the project’s course, both these challenges has
delayed the publication of some of the cross-strand work.
The neutron-scattering programme (SANS-mapping of flow with multiscale modelling), was delayed by several months
when the original sapphire-windowed cell failed to withstand the pressures required to reach non-linear flow. The
choice of sapphire was motivated by the requirement to make birefringence measurements as well. This was overcome
by building an aluminium-windowed SANS cell, and an identical quartz-windowed birefringence cell. Again, this has
affected the most optimistic publication schedule somewhat, but not the acquisition of results.
Some redistribution of human resources was made within the project. A studentship originally allocated to Durham was
moved to Sheffield to take advantage of the flow crystallisation programme when all synthesis and scattering tasks were
being covered but PDRA resources at Durham.
The industrial financial contribution was essential to the project as a flexible instrument. Bizarrely, EPSRC had only
chosen to fund half of the PDRA resources planned at the essential flow-visualisation groups of Cambridge and
Bradford. The resources for this task, central to the whole project, had to be made good by the industrial funding, as did
the solid-state investigations at Leeds. But this case at the cost of a PDRA originally allocated to industrial liason and
satellite projects. This lack was made good by allocating special responsibility where possible to PDRAs within the
project, to maintain regular links with participating companies.
Research Impact and Benefits to Society
The influence of the project has been very great indeed. It has certainly changed the way that academic-industrial
research is done in polymer processing in the UK, and has attracted considerable international attention. Perhaps the
clearest signal of the impact of the project was the strongly-voiced request by the industrial consortium that the
collaboration continue to tackle the new challenges posed three-years on, and their willingness to support this by further
cash and kind contribution. Collaborators have also, naturally, been industrial co-authors on some of the project
7
publications. The international profile of the project has also attracted new industrial participants, and in an application
under development and discussion with EPSRC programme managers at the moment, we will include ICI, Crown Cork
and Seal and Bayer as members. At the penultimate meeting of the consortium, we asked the original members to
provide a SWOT analysis of the project. Their summary comments were:
 exceptional vision – to propose such an ambitious project and turn it into a reality
 unique achievement – to gather the leading academic specialists and integrate into a team
 development of a range of “tools”
 exceptional organisation and communication (meetings, website, flow of materials and data .. ) the spirit and
pleasure of the meetings
Publication and Presentation
The project has enjoyed a very high international impact. Nothing of its kind has been attempted in the USA. Similar
projects in continental Europe do not emphasis the key molecular science, and the corresponding aspects of the Doi
project in Japan have only very recently turned to non-linear response. Conference and publication coverage is
increasing rapidly, including an invited series of papers in the leading Journal of Rheology and papers in Physics
Review Letters. The “flagship” paper on SANS flow-mapping and length-scale dependent orientation is currently
accepted for publication by the journal Science. The principle investigator has written by invitation an issue of
Advances in Physics covering the field of molecular polymer dynamics. Invited lectures on the science of the
collaboration have been given by all the co-investigators at international conferences in Vancouver, San Francisco,
Brisbane, Erlangen, Cambridge, Eindhoven, Santa Barbara, Ventura.
Training
The training achievements of research staff both in the academic and industrial partners have been of especial impact.
One of the project’s post doctoral research assistants (Heeley) has since been appointed to a lectureship in Sheffield
(Heeley) and another (Likhtman) was awarded a 5-year EPSRC Advanced Fellowship. Another (Nicholson) has moved
to start an academic group in the field in Australia, and remains a strong collaborator. Two of the co-investigators have
been awarded international prizes in the course of their work. Awareness of the project has been maintained over a
wider sector of industrial users via links to the EPSRC project EPP, the network COMPPRO and the White Rose DTI
Faraday centre on packaging technology. Joint personnel have been established with all of these related projects. A
wider network still is informed by the regular newsletters, which enjoy a circulation of 500.
Public Understanding of Science
The X-ray scattering during crystallisation experiment appeared in the first of the 2002 Royal Institution Christmas
Lectures by Prof Tony Ryan (Sheffield) which was recorded in front of a live audience of 450 on December 11 and
broadcast on December 26 to TV audience of 1 million viewers. The televised lecture featured a web-link to the ESRF
experiment after a description of how synchrotron radiation was enabling the development of better consumer products
through the understanding of crystallisation processes. To a rather smaller audience, in 2000, Prof. Tom McLeish
(Leeds) and Dr. Bill McDonald (Du Pont Teijin) were featured on BBC Radio4’s Material World with Quentin Cooper,
talking about the impact that moelcular science was having on industrial materials development. Several schools and
public talks have also been given by members of PP.
The Global Picture
Naturally this work takes place in a global context, although it is significant that for the specifically molecular aspects
of research and development, companies with a global reach have chosen to invest in the PP team for their knowledge
transfer.
In Europe, key developments in flow-field appraisal or models of LCB polymers have been made at TuE
Eindhoven [6,7] using cross-slot flows. They have found that the constitutive equation fro branched polymers
developed at Leeds within PP fares far better than any others [7,9]. Recent work there has made considerable strides
in understanding toughness in glassy polymers [8] from their molecular characteristics, but lacks data on monodisperse
materials. In a wider European context, the Framework V project in closest spirit to PP (apart from the project LCB
Polyolefins, which preceded it and contributed some of the early materials) was the complex-flow modelling
consortium ART (“Advanced Rheological Tool”). Restricting their modelling to phenomenological constitutive
equations, the conclusion of this project was that better molecular-based equations would be needed to realise its goal.
The group in Naples has developed an alternative attack on the strong-flow melt physics of “Convective Constraint
Release” of the recent PP work [10]
In North America, molecular rheology has been the focus of several strong groups. In Michigan, a semiempirical approach is being applied to bimodal blends [11]. In Cornell, comb-like architectures are also under
investigation [12]. In Santa Barbara experiments on entangled solutions are complementary checks on the theoretical
developments to those on melts [13]. Both of the latter two groups, as well as the Leeds team within PP, have shared
data and materials with Tam Sridhar, in Melbourne, who is an expert on extensional rheology of solutions [14].
8
Experimental rheology of the new LCB melts is the subject of programmes in Virginia [15] and Montreal [16] Both of
these groups have approached the principle investigator for collaboration using US/EU and Canadian resources. The
anticipated development of a flow-scale model for semi-crystallising polymers has been the focus of a series of papers
from another group in Cornell [17], reinforcing the anticipated need for data on monodisperse materials we articulated
in the proposal for PP1. Recent observations from the Caltech group underline the need to connect the molecularlevel and process levels in a single collaboration [18].
In Japan, research towards the multiscale modelling approach we have taken has been concentrated in the
MITI-funded “Doi Project”, based in Nagoya. The results of the project, a set of modelling software known as OCTA,
is available globally as freeware [19]. There is nothing in the suite resembling the PP programmes FlowSolve and
FlowDis, but an imaginative stochastic “slip-link” model of an entangled polymer has shed light on recent experiments
on the model star-architecture melt [20][P16].
The molecular aspects of the field were discussed intensively for a month during a recent workshop at the
Kavli Institute of Theoretical Physics, UC Santa Barbara. The 25 international participants included five from the PP
team, and the workshop was organised by the principle investigator. The very rapid exposure of recent developments
have set a very fresh and urgent agenda for the field, in which increasingly the deepest scientific questions (“how do
entanglement fields deform at high strain?”) impinge directly on industrial challenges (“How do we increase the melt
strength of our new family or resins?”). The UK consortium is very well placed with both strong international links and
internal complementarity, to take on the new tasks.
Some powerful international collaborations were initiated from the PP work, not foreseen at the outset, but
which have contributed to it. The unique neutron spin-echo (NSE) programme at Jülich madea natural complement to
the molecular theory of chain dynamics from strand II ([P15]), and the stretch/quench apparatus of that group has
provided different measurements to ours in SANS on model LCB materials ([P17]). The non-linear extension to the
theory was made with the most helpful collaboration of Dr. Scott Milner of Exxon ([P5], [P6], [P21]). The KITP
workshop produced a joint publication aimed at clarifying some of the ambiguous definitions that have emerged in the
field [(P20)]. The rheology group at Erlangen has started sending us their experimental data to compare with the PP
molecular models. The PP project has assisted in creating a long-term collaboration between the Sheffield group and
Dr. Wim Bras of the DUBBLE beamline at ESRF, with collaborative plans to build further process on-line devices. As
a result of contacts with the Dutch group at Eindhoven, the Leeds group has (unusually) been invited to become
members of the Dutch Polymer Institute (DPI), and has received 2 years PDRA funding for further work on commercial
LCB polymers.
Explanation of Expenditure
There was no change to the anticipated spend of the grant, except those minor changes detailed above in the project
plan. The industrial financial support was used mainly to support the PDRA positions essential to the project but not
funded in full by EPSRC in Cambridge, Bradford and Leeds. Additional support was given to cover extensions of key
PDRA so that where possible, the termination of the grants at the various institutions could be uniform. This has
amounted to up to 3 months of personnel spend at Cambridge, Sheffield, Oxford and Leeds. 3 months total extension
was granted to two PDRAs at Leeds from a previous EU project that contributed materials to PP, so that integration
was as smooth as possible.
Further Research or Dissemination Activities
In the publication list will be found several key works in preparation at this stage. Others will also emerge, but we
include only those for which results are at hand and titles planned. For over a year, a successor project to PP has been
in planning. It comes at the strong request of the industrial consortium as well as the academic group, who have found
in the collaboration and methodology a uniquely powerful way of working. If the new project is granted, and when a
few more of the exciting cross-strand results are in press, we plan a public, London-based meeting for the press, DTI
and industry to “showcase” the project team, results and promise.
In the meantime, there are several other avenues for further research activities. Large subgroups of the collaboration are
involved with EU FWVI “Networks of Excellence” that have been retained to the final evaluation round. One will
make use of the multiscale modelling approach we have developed.
The software flow modelling tools flowSolve and its data-mining link flowDis, together with the constitutive tools PomPom and ROLIPOLY clearly constitute a very useful package for industry. As a next stage, it is very urgent that the
progress made in understanding the crystallisation in flow of the PE-like materials be embodied into this flow-solver.
This, and the natural 2-phase flow requirement that it generates, will form a central plank of further research plans of
the consortium.
9
ANNEX: PUBLICATION LISTS
General References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
PEG-EPSRC York Meeting November 1997; Plastics Processing in the UK, DTI, 1996
D.C. Fisher in Metallocene-Catalysed Polymers:Materials, Properties, Processing and Markets, SPE, 1998
Polypropylene Films, 1996-2001, North America, Europe, & Japan, report of Chemical Market Resources,
Inc., Houston, TX (1996).
High EVA Copolymers, North America, Europe, & Japan-1996-2001, report of Chemical Market Resources,
Inc., Houston, TX (1997).
M. Doi and S.F. Edwards, The Theory of Polymer Dynamics, Oxford (1986).
W. Verbeeten, PhD Thesis, TuE, Eindhoven (2001)
Verbeeten, W.M.H., Peters, G.W.M. and Baaijens, F.P.T., J. Rheol., 45, 823 (2001)
H.E.H. Meijer, GRC in Polymer Processing, Ventura, CA (2003).
R.J. Blackwell, T.C.B. McLeish and O.G. Harlen, “Molecular Drag-Strain Coupling in Branched Polymer
Melts” J. Rheol., 44, 121-136 (2000).
G. Ianniruberto and G. Marrucci, “A simple constitutive equation for entangled polymers with chain stretch”,
J. Rheol., 45, 1305 (2001)
C. Pattamaprom and R.G. Larson, “Constraint Release Effects in Monodisperse and Bidisperse Polystyrenes in
Fast Transient Shearing Flows”, Macromolecules, 34, 5229 (2001)
Mohammad T. Islam, Juliani, Lynden A. Archer and Sunil K. Varshney, Macromolecules, 34, 6438 (2001)
J. Oberhauser and L.G. Leal, work in preparation for publication.
X. Ye, R. G. Larson, C. Pattamaprom and T. Sridhar , “Extensional properties of monodisperse and
bidisperse polystyrene solutions”, J. Rheol, to appear (2003)
D. Baird, Macromolecules, 35, (2002).
P. Wood-Adams and S. Costeaux, “Thermorheological Behavior of Polyethylene: Effects of Microstructure
and Long Chain Branching”, Macromolecules, 34, 6281 (2001)
M. Islam and A. J. McHugh, J. Rheol., 45 (2003)
J. A. Kornfield, G. Kumaraswamy, and A. M. Issaian, "Recent Advances in Understanding Flow Effects on
Polymer Crystallization," Industrial & Engineering Chemistry Research, in press (2002).
www.octa.jp
Shanbhag, S., Larson, R.G., Takimoto, J.And Doi, M, Phys. Rev. Lett., 87, 195502 (2001).
10
Publications Arising from PP
P1.
P2.
P3.
P4.
P5.
P6.
P7.
P8.
P9.
P10.
P11.
P12.
P13.
P14.
P15.
P16.
P17.
P18.
P19.
P20.
P21.
P22.
P23.
P24.
P25.
P26.
C. M. Fernyhough, R. N. Young, D. Poche, A. W. Degroot, F. Bosscher, “Synthesis and Characterization of
Polybutadiene and Poly(ethylene-1-butene) Combs, Macromolecules, 34, 7034 (2001)
K. Lee, M.R. Mackley, T.C.B. McLeish, T.M. Nicholson and O.G. Harlen, “Experimental observation and
numerical simulation of transient stress fangs within flowing molten polyethyelene”, J. Rheol., 45, 1261-1277
(2001).
J. Crosby, M. Mangnus, W. de Groot, R. Daniels, and T. C. B. McLeish, “Characterisation of long chain
branching: dilution rheology of industrial polyethylenes”, J. Rheol. 46, 401 (2002).
J. Read and T. C. B. McLeish, “Molecular Rheology and Statistics of Long Chain Branched MetalloceneCatalyzed Polyolefins”, Macromolecules, 34, 1928-1945 (2001).
A.E. Likhtman, T.C.B. McLeish and S.T. Milner, “Microscopic Theory for the Fast Flow of Polymer Melts”,
Phys. Rev. Lett., 85, 4550-4553 (2000).
S.T. Milner, T.C.B. McLeish and A.E. Likhtman, “Microscopic Theory of Convective Constraint Release”, J.
Rheol., 45, 539-563 (2001).
R.J. Blackwell, O.G. Harlen and T.C.B. McLeish, “Theoretical Linear and Nonlinear Rheology of Symmetric
Treelike Polymer Melts, Macromolecules, 34, 2579-2596 (2001).
D. R. Daniels, T. C. B. McLeish, B. J. Crosby, R. N. Young, and C. M. Fernyhough, “Molecular Rheology of
Comb Polymer Melts 1. Linear Viscoelastic Response”, Macromolecules, 34, 7025-7033 (2001).
R.S. Graham, T.C.B. McLeish and O.G. Harlen, “Using the Pom-Pom Equations to Analyze Polymer Melts in
Exponential Shear”, J. Rheol., 45, 275-290 (2001).
A. Pryke, R.J. Blackwell, T.C.B. McLeish and R.N. Young, “Synthesis, hydrogenation and rheology of 1-2
polybutadiene star polymers”, Macromolecules, 35, 467-472, (2002).
M. Collis, A. Lele, M.R. Mackley, R.S. Graham, D.J. Groves, A. E. Likhtman, T.M. Nicholson, O.G. Harlen,
T.C.B. McLeish, L. Hutchins, C. Fernyhough and R.N. Young, “Constriction Flows of Monodisperse Linear
Entangled Polymers: Flow Visualisation and Molecular Modelling”, J. Rheol, submitted (2003)
R.J. Blackwell, T.C.B. McLeish and O.G. Harlen, “Molecular Drag-Strain Coupling in Branched Polymer
Melts” J. Rheol., 44, 121-136 (2000).
E. Likhtman and R. S. Graham, “Simple Constitutive Equation for Linear Polymer Melts Derived from
Molecular Theory: the ROLIEPOLY Equation”, J. Non-Newt. Fluid Mech. (2003) in press
E. Likhtman and T.C.B. McLeish, “Quantitative Theory for Linear Dynamics of Linear Entangled Polymers”,
Macromolecules, 35, 6332-6343 (2002).
Wischnewski, M. Monkenbusch, L. Willner , D. Richter, A.E Likhtman, T.C.B. McLeish, B. Farago, “Molecular
observation of contour-length fluctuations limiting topological confinement in polymer melts”, Phys. Rev. Lett.,
88, 058301 (2002).
Frischknecht, A. L.; Milner, S. T.; Pryke, A.; Young, R. N.; Hawkins, R.; McLeish, T. C. B., “Rheology of
Three-Arm Asymmetric Star Polymer Melts”, Macromolecules, 35, 4801-4820 (2002).
M. Heinrich, W. Pyckhout-Hintzen, J. Allgaier, D. Richter, E. Straube, D. J. Read, T. C. B. McLeish, D. J.
Groves, R. J. Blackwell and A. Wiedenmann, “Arm Relaxation in Deformed H-Polymers in Elongational Flow
by SANS”, Macromolecules, 35, 6650-6664 (2002).
T.C.B. McLeish, “Why, and when, does dynamic tube dilation work for stars?”, J. Rheol., 47, 177-198 (2003).
Suneel, R. S. Graham, and T.C.B. McLeish, “Characterisation of an Industrial Polymer Melt Through either
Uniaxial Extension or Exponential Shear Data: An Application of the Pom-Pom Model”, Appl. Rheol. 13, 19-25
(2003)
R.G. Larson, T. Sridhar, L.G. Leal, G.H. McKinley, A.E. Likhtman and T.C.B. McLeish, “Definitions of
entanglement spacing and time constants in the tube model”, J. Rheol., 47, 809-818 (2003)
S. Graham, A. E. Likhtman, T. C. B. McLeish and S.T. Milner, “Microscopic theory of linear, entangled
polymer chains under rapid deformation including chain stretch and convective constraint release”, J. Rheol,
(2003) in press
R.W. Richards, J. Bent and T. Gough, “A Recirculating Flow Cell for SANS during Polymer Extrusion”, Rev.
Sci. Inst., submitted (2003)
E.L.Heeley, Maidens AM, Olmsted PD, Bras W, Dolbnya IP, Fairclough JPA, Terrill NJ, Ryan AJ, “The early
stages of crystallization in isotactic polypropylene”, Macromolecules, 36, 3656–3665 (2003)
Heeley EL, Poh CK, Li W, Maidens A, Bras W, Dolbnya IP, Gleeson AJ, Terrill NJ, Fairclough JPA, Olmsted
PD, Ristic RI, Hounslow MJ, Ryan AJ, “Are metastable, precrystallisation, density-fluctuations a universal
phenomenon?”, Faraday Discussions, 122, 343-361 (2003).
Heeley EL, Morgovan AC, Bras W, Dolbnya IP, Gleeson AJ, Ryan AJ, “Shear-induced crystallization of
polyethylene studied by small- and wide-angle X-ray scattering techniques”, Phys. Chem. Comm., 158-160 Oct
17 (2002).
Bras, I.P. Dolbnya, D. Detollenaere, R. van Tol, M. Malfois, G.N. Greaves, A.J. Ryan and E. Heeley, Recent
experiments on a small-angle/wide-angle X-ray scattering beamline at the ESRF, J. Appl. Cryst., 36, 791–794
(2003).
11
P27.
P28.
P30.
P31.
P32.
P33.
P34.
P35.
P36.
P37.
P38.
P39.
P40.
P41.
P42.
P43.
P44.
Heeley EL, Bras W, Dolbyna IP, Maidens A, Olmsted PD, Fairclough JPA, Ryan AJ, “Evidence of spinodal
decomposition in semi-crystalline polymers”, Fibre Diff. Rev., 10, 63-71 (2002).
Morgovan AC , Heeley EL, Fernyhough CM, Bras W, Terrill NJ and Ryan AJ, “Quiescent crystallization of
hydrogenated polybutadienes with novel architectures, using Small- and Wide-Angle X-ray Scattering and DSC
techniques”, Phys. Chem. Comm, submitted (2003).
J. Bent L. R. Hutchings, R. W. Richards, T. Gough, R. Spares, P. D. Coates, I. Grillo, O.G. Harlen, D.J. Read,
R.S. Graham, A.E. Likhtman, D.J. Groves, T.M. Nicholson, T.C.B. McLeish, “Neutron-Mapping Polymer Flow:
Scattering, Flow-Visualisation and Molecular Theory”, Science, under review (2003).
M. Collis et al., “Contraction/Expansion flows of Model Branched Polymers: Experiment and Molecular
Modelling”, J. Rheol, in preparation (2003)
R.S. Graham et al., “Contraction/Expansion flows of Model Polymer Blends: Experiment and Molecular
Modelling”, J. Rheol, in preparation (2003)
J. Embery and R.A. Duckett, “Dependencies on fracture mechanism in isotropic and oriented Polystyrene”, in
preparation (2003).
J. Embery and R.A. Duckett, “Mechanical properties of Hot Drawn isotropic and oriented Polystyrene”, in
preparation (2003).
J. Embery and R.A. Duckett, “Cold rolling of PS to high orientation”, in preparation (2003)
J. Wu, P. Buckley, J. Bent, R.W. Richards, M. Collis, Y. Chen, M.R. Mackley, T.M. Nicholson, D.J. Groves,
O.G. Harlen, A.E. Likhtman, R.S. Graham, J. Embery, R.A. Duckett, T.C.B. McLeish, “Extrusion and Draw of
Model Monodisperse Polystyrene Melt: Flow-visualisation, Neutron Scattering and Theory” in preparation
(2003).
J. Wu, P. Buckley, M. Collis, Y. Chen, M.R. Mackley, T.M. Nicholson, D.J. Groves, O.G. Harlen, A.E.
Likhtman, R.S. Graham, T.C.B. McLeish, “Extrusion and Draw of Model Monodisperse Polystyrene Melt: Solid
State Constitutive Behaviour” in preparation (2003).
D. DeFocatiis, P. Buckley, J. Embery, R.A. Duckett, M. Collis, Y. Chen, M.R. Mackley, T.M. Nicholson, D.J.
Groves, O.G. Harlen, A.E. Likhtman, R.S. Graham, T.C.B. McLeish, “Extrusion and Draw of Model
Monodisperse Polystyrene Melt: Fracture and Environmental Stress Cracking” in preparation (2003).
R.S. Graham et al, “SANS-Mapping of Molecular Polymer Flows: Molecular weight and Strain Rate Effects”,
Macromolecules, in preparation (2003).
J. Bent et al., “SANS Measurements of a Bimodal Polymer Melt in Flow”, in preparation (2003).
D.J. Groves et al., “Step-rate Effects in Polymer Melt Damping Functions: Experiment and Molecular Theory”,
J. Rheol., in preparation (2003)
T.M. Nicholson, O.G. Harlen, M. Collis, M.R. Mackley, T.C.B. McLeish, “A Constitutive Instability in
Contraction Flows of Monodisperse Polymer Melts: Experiment and Simulation”, in preparation (2003)
A. L. Gott, P. C. McGowan, T.J. Podesta and M. Thornton-Pett, “Pendant Arm N-monofunctionalised 1,4,7Triazacyclononane of Fe(II) and Ru(II) Fragments”, Jnl. Chem. Soc,Dalton Trans., 3619 (2002)
T.M.Nicholson, P.S. Hope, D.J. Groves, M. Martyn, P.D. Coates and T.C.B. McLeish, “Molecular Modelling of
Die-Swell in HDPE Resins”, J. Rheol., in preparation (2003)
12
Conference Presentations from MuPP
Pr1.
Pr2.
Pr3.
Pr4.
Pr5.
Pr6.
Pr7.
Pr8.
Pr9.
Pr10.
Pr11.
Pr12.
Pr13.
Pr14.
Pr15.
Pr16.
Pr17.
Pr18.
Pr19.
Pr20.
Pr21.
Pr22.
Pr23.
Pr24.
Pr25.
Pr26.
Pr27.
Pr28.
Pr29.
T.C.B. Mcleish and D.J. Read, “Molecular Constitutive Equations for Branched Polymer Melts”, International
Congress on Rheology, Cambridge (2000)
T.C.B. McLeish, O.G. Harlen and T.M. Nicholson, “Molecular Polymer Processing”, EPF Eindhoven, (2001)
T.C.B. McLeish and D.J. Read, “Molecular Modelling of LCB Metallocene Rheology”, Society of Rheology,
Hilton Head 2001
T.M. Nicholson, O.G. Harlen and T.C.B. McLeish, “The Microscale Polymer Processing Project”,Vancouver,
(2002)
R.S. Graham, “CCR-Stretch Tube Model of Entangled Polymers”, KITP Programme, Santa Barbara, (2002)
A.E. Likhtman, “High Dimensional Activated Processes”, KITP Programme, Santa Barbara, (2002)
T.C.B. McLeish , “The Microscale Polymer Processing Collaboration”, Chem. Eng. Seminar, Santa Barbara,
(2002).
Spares, R, Gough, T, Martyn, MT, Olley, P and Coates, PD (2001), Flow visualisation of polymer melt
contraction flows for validation of numerical simulations. SPE Antec (2001), Dallas, US.
Gough, T, Martyn, MT, Spares, R and Coates, PD (2001), Small scale flow visualisation of polymer melts in a
recirculation extruder. SPE Antec 2001, Dallas, US.
Gough, T, Martyn, MT, Spares, R and Coates, PD (2001), Small scale flow visualisation of polymer melts in a
recirculation extruder. PPS 17, Montreal, Canada.
Gough, T, Spares, R, Martyn, MT and PD Coates (2002), Full field stress and velocity measurements for
polymer melts in extrusion dies. SPE Antec 2002, San Francisco, US.
Gough, T, Spares, R, Martyn, MT, Bent, J and PD Coates (2002), Full field stress and velocity measurements
for polymer melts in extrusion dies. PPS 18, Guimarães, Portugal.
Bent, J, Richards, RW, Gough, T, Spares, R and PD Coates (2002), The molecular conformation of
polystyrene during flow through a slot die. PPS 18, Guimarães, Portugal.
McLeish, TCB, Hutchins, L, Richards, RW, Bent, JF, Gough, T, Coates, PD, Nicholson, T, Likhtman, A and
Graham, R (2002), Neutron scattering from melts in complex flows. 74th annual meeting of the Society of
Rheology.
Gough, T, Spares, R, Martyn, MT, Bent, J, Heeley, E and Coates, PD (2003). Small-scale studies of flowing
polymer melts inside recirculating flow cells. Antec 03, Nashville, US.
Gough, T, Spares, R, Martyn, MT, Bent, J and PD Coates (2002), Full field stress and velocity measurements
for polymer melts in extrusion dies. PPS 18, Guimarães, Portugal.
Bent, J, Richards, RW, Gough, T, Spares, R and PD Coates (2002), The molecular conformation of
polystyrene during flow through a slot die. PPS 18, Guimarães, Portugal.
McLeish, TCB, Hutchins, L, Richards, RW, Bent, JF, Gough, T, Coates, PD, Nicholson, T, Likhtman, A and
Graham, R , Neutron scattering from melts in complex flows. 74th annual meeting of the Society of Rheology,
Minneapolis (2002)
Bent, JF, Richards, RW and Gough, T (2003), A recirculation cell for the small-angle neutron scattering
investigation of polymer melts in flow. Submitted to Review of Scientific Instrumentation.
Gough, T, Spares, R, Martyn, MT, Bent, J, Heeley, E and Coates, PD (2003). Small-scale studies of flowing
polymer melts inside recirculating flow cells. Antec 03, Nashville, US.
Gough, T, Spares, R, Martyn, MT, Bent, J, Heeley, E and Coates, PD (2003). Small-scale studies of flowing
polymer melts inside recirculation flow cells. PPS 19, Melbourne, Australia
Bent, JF, Hutchings, LR, Richards, RW, Gough, T and Grillo, I (2002). A molecular description of extrusion.
Annual Report of the ILL – Scientific Highlights - Soft Matter. Institut Laue-Langevin, Grenoble, France.
http://www.ill.fr/AR-02/AR_2002.pdf p.66.
T.C.B. McLeish, Molecular Theory of Entangled Polymers, Wohl Award lecture, Delaware, (2003).
McLeish, TCB, Hutchins, L, Richards, RW, Bent, JF, Gough, T, Coates, PD, Nicholson, T, Likhtman, A and
Graham, R , Neutron scattering from melts in complex flows. GRC Polymer Processing, Ventura (2003)
Wu, J.J. and Buckley, C.P. “Deformation modelling of glassy polymers incorporating structural change” SPE
ANTEC, San Francisco, 2002.
Wu, J.J. and Buckley C.P. “The role of molecular parameters in the plastic deformation of glassy polystyrene”
12th International Conference on Deformation Yield and Fracture of Polymers, Cambridge, April 7-10, 2003.
Buckley, C.P. and Wu, J.J. “Anisotropic plastic deformation of glassy polymers with process-induced
molecular orientation” to be presented at the 19th Annual Meeting of the Polymer Processing Society,
Melbourne, July 7-10, 2003.
Buckley, C.P. and DeFocatiis, D. “Environmental stress crazing of polystyrene: effects of chain-length and
process-induced chain orientation” to be presented at the 26th Australasian Polymer Symposium, Noosa, July
13-17, 2003.
M.R. Mackley, “The multipass rheometer; design and application ”, 6th European Conference of Rheology,
Erlangen (2002).
13
Pr30.
Pr31.
Pr32.
Pr33.
Pr34.
Pr35.
Pr36.
Pr37.
Pr38.
Pr39.
Pr40.
Pr41.
Pr42.
Pr43.
Pr44.
Pr45.
Pr46.
Pr47.
Y Chen, M R Mackley and T Nicholson, The quantification and numerical simulation of the processing
behaviour for small quantities of molecularly tailored polystyrene”, 6th European Conference of Rheology,
Erlangen (2002)
M W Collis and M R Mackley, The comparison of flow simulation for mono and polydisperse polymer melts
with laboratory flow birefringence studies, 6th European Conference of Rheology, Erlangen (2002).
M W Collis and M R Mackley, Comparison of numerical simulations with experimental flow birefringence
studies on mono- and poly-disperse polymer melts, INNFM Conference on Process Modelling, Lake Vrynwy
(2003)
M W Collis and M R Mackley, Laboratory Polymer Processing Experiments using Small Material Quantities,
18th Polymer Processing Society Meeting, Guimarães, Portugal (2002)
A.E. Likhtman, R.S. Graham, T.C.B. McLeish, How to get Simple Constitutive Equations for Polymer Melts
from Molecular Theory, , 6th European Conference of Rheology, Erlangen (2002).
R.W. Richards, J. Bent, SANS on Extruding Polymer Melts, 18th Polymer Processing Society Meeting,
Guimarães, Portugal (2002). “Flow induced crystallisation” Ellen Heeley poster presented at Collaborative
Computing Project (CCP13) Meeting, Keele, (2002)
A. Morgovan “Crystallisation in comb polymers” poster presented at Collaborative Computing Project
(CCP13) Meeting, Keele, (2002)
AJ Ryan, “Are Precrystalline Density Fluctuations a Universal Phenomenon?” Faraday Discussion 122,
Manchester, (2002)
E. Heeley “Effects of shear flow on the crystallisation of commercial polymers” Faraday Discussion 122,
Manchester, (2002)
A. Morgovan, “Crystallisation of comb polymers and their blends”, Faraday Discussion 122, Manchester,
(2002)
AJ Ryan, “Crystallisation in Block Copolymers and their Blends” ACS Meeting Orlando, USA,
A.J. Ryan“Crystallisation in Block Copolymers and their Blends” Synchrotron Radiation in Materials Science3, Singapore, (2002).
AJ Ryan “Crystallisation in Block Copolymers and their Blends”, WE & A Hereaus Seminar, Waldau,
Germany, (2001).
AJ Ryan “Crystallisation in Block Copolymers and their Blends” IUPAC Symposium on Scattering from
Polymers, Prague, (2001).
E. Heeley, “Can flow create nuclei?” Collaborative Computing Project (CCP13) Meeting, Stirling, (2001)
A. Morgovan “Synthesis and characterisation of comb polymers”, Collaborative Computing Project (CCP13)
Meeting, Stirling, (2001)
C. Ferneyhough, “Synthesis and charaterisation of comb polymers”, EPF Eindhoven, (2001)
T.M.Nicholson, Molecular Multiscale Modelling of Controlled architecture Polymers to be presented at the
19th Annual Meeting of the Polymer Processing Society, Melbourne, July 7-10, 2003.
14