UNIVERSITY OF BRADFORD

Faculty of Engineering & Informatics

CPE7012-B: Polymer Engineering.

Coursework assignment 2020

The Manufacture and Characterisation of Controlled Rheology

Polypropylenes (CRPP) by reactive processing with peroxide

Introduction
The increasing performance requirement of polymers is driving research for more efficient and cost-
effective solutions for their manufacture. Development of new resin systems to meet demands for
high performance materials would undoubtedly take too long and would certainly be too expensive
since it would require huge investments in totally unexplored technologies and new plant facilities.
Instead, polymer resin manufacturers have recently started to use extruders as chemical reactors.

The process allows the tailoring of molecular structure to give polymers with specific
rheological/mechanical properties. The practice of combining polymer extrusion processing with
polymer reactions in one operation is known as reactive extrusion (REX). REX processing is used in
industry to modify molecular structure of extruded polymer products. REX technology is exploited in
the production of different grades of controlled rheology polypropylenes (CRPP) from a single high
molar mass feedstock. CRPP’s are suitable for high-speed manufacture of synthetic fibres, thin films
and thin walled moulded parts with different mechanical properties.

This coursework assignment involves several practical elements. Students will not only manufacture
a series of controlled rheology polypropylenes but also conduct a series of characterisation
techniques that link change in molecular structure with rheological and mechanical properties.

Aims

To provide students with practical experience in the operation of polymer conversion processes and
characterisation techniques.

The learning outcomes of this coursework are to:

 Develop knowledge on current technologies and practices of REX processing via lecture
notes and researching literature.
 Gain practical experience of REX processing in the laboratory using twin screw compounding
to create REX processed polypropylene.
 Develop experience of using analytical techniques and instruments to characterise the
mechanical, rheological and thermal properties of these CRPP samples.
 Develop skills in technical report writing.

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Experimental:
Materials:
Polypropylene: Sabic 531P ( MFI ~ 0.3)
Peroxide : Aldrich Dicumyl peroxide ( DCP). 1.56 g/cc

Pre-blending:

NOTE: Read the safety notes at the end of this document with regards to safety in handling
peroxides. Create dry pre-blends of the compounds given in Table 1 below (to save time, and reduce
risk, these pre-blends may be given to the students). Weigh out 1500 g of polypropylene pellets and
place in a polyethylene bag. Weigh out the appropriate masses of the peroxide powder in a fume
cupboard (Clean room area WB13). Add the powder to the 1500 g batches of PP pellets. Shake each
bag for 5 mins to get even distribution / coating of the fine peroxide powder on the pellets.

Extrusion Compounding:

Use the Thermo-Scientific twin screw compounding extruder in lab area WB10, (useful to take
pictures of the equipment to include in your report). Note a typical screw configuration for this
machine will be available for you to view. You should identify the main features of the screw. The
extruder is fitted with a 3 strand lace die.

H&S: make sure the LEV is over the die exit of the machine and any students handling the pre-blend
composition must wear dust masks.

Parameters- Temp profile : throat water cool, 160C, 180C, 200C, die 200C. Set the screw rotation
RPM to: 250

Process the compositions in the sequence shown in Table 1. The compounds are added sequentially,
starting with the low dose peroxide. The pre-blends are poured straight into the loss in weight
Montan hopper. This is set at 5 Kg /hr once stable processing is established. Add further compounds
when there is only 0.1Kg registering as the mass left in the hopper. The Montan hopper is used
control the delivery of pellets to the throat of the extruder. Allow 10 minutes of purging between
batch collections. Extruded strands are fed through the water bath and the air blade drier at the end
of the bath. Feed the strands into the pelletiser set at a speed to 3.0 this should result in pellets of ~
3mm length. Collect each batch of compound in a polythene bag in the basket beneath the unit. The
pelletising process may need one student dedicated to ensure there is no slippage on feed wheel.
You will need approximately 1 Kg of each compound. Repeat the extrusion process with each batch.

Formulations: Table 1. Compositions for processing

Material Mass PP Mass % Torque Pressure

( nominal compositions) ( g) DCP (g) DCP ( Nm) (Bar)
PP 531P 1500 0.0 0.0
PP 531P + 05% DCP 1500 0.75 0.05
PP 531P + 0.1% DCP 1500 1.5 0.1
PP 531P + 0.15% DCP 1500 2.25 0.15

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Extrusion Observations:

Comment on any visual observations made during the extrusion process. Also check and write down
any machine torque/ die pressure measurements for each batch. Such observations may provide
qualitative information to reinforce data from characterisations tests.

Injection Moulding:

Use the Fanuc i-2000 injection moulding machine located in lab area WB9. The moulding parameters
on the machine will be set ready for the injection moulding of these compounds. The test piece will
be in the form of an ISO standard tensile bar.

A minimum of 15 test bars are required for each batch. Record of the mass of the samples,
sequentially, during the injection process.

Injection moulding Observations:

Comment on any visual observations made during the injection process. Also check and write down
any machine parameters used for each batch - look at the pressure profiles and peak pressure of
the materials.

Characterisation:
Compounding: comment on any visual observations made during the extrusion process. Also check
and write down any machine torque/ pressure measurements for each batch.

Gel Permeation Chromatography :– a procedure and the chromatograms of ‘similar’ REX processed
polypropylene samples are attached.

Rheometry:

Dynamic : Use an Anton Paar model M501 rotational rheometer located in lab area WG21. Set the
instrument to an operating temperature of 230C. Use the 25 mm parallel plate system with a 1%
strain, from 0.001 to 100 rad/s frequency sweep. Data collected and filed under Laboratory Tasks-
coursework.

Note the virgin 531P PP is evaluated along with processed + 0.0% peroxide composition so that a
base line can be established to evaluate of processing alone on the properties of a virgin
polypropylene. The added effect of peroxide only induced changes can then be noted. (Some
polymers are sensitive to processing owing to mechanical or thermal degradation during the
process ).

MFI: Use a Kayness MFI instrument. Data from this instrument can be used as a qualitative measure
of a change in melt viscosity. Use 2.16kg mass and set temperature of 230◦C. (The method is
described in the similar standards ASTM D1238 and ISO 1133).

Procedure for Polypropylene:

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 1. The apparatus consists of a small calibrated die inserted into the apparatus, with the length
= 8 mm and diameter = 2.095 mm.
2. Take about 4 to 5 grams of polymer and pack it properly inside the barrel using the
appropriate tool to avoid formation of air pockets.
3. Introduced the piston on top of the sample. The piston is used to extrude the molten
polymer through the die.
4. Allow the sample to preheat for 6 min at 230°C for polypropylene.
5. After the preheating the 2.16kg weight is placed onto the piston.
6. The weight exerts a force on the molten polymer and it immediately starts to extrude
through the die.
7. Only collect the mass of extrudate when the piston position is between the graduated marks
scribed on the outside of its diameter.
8. Start the timer and collect a sample of the melt over the 6 minute period. Note for high MFI
melts this time may have to be reduced to 2 or 1 minute.
9. Accurately weigh the mass collected.
10. MFI is expressed as grams of polymer/10 minutes.

Synonyms of Melt Flow Index are Melt Flow Rate and Melt Index. More commonly used are their
abbreviations: MFI, MFR and MI.

Thermal Characterisation:

Use the TA Instruments model Q20 DSC located in lab area WG21 . Cut small samples ( ~ 10 – 20
mg) from the REX processed materials and produce thermograms ( heat Flow v’s Temperature) for
the samples. Recommend taking the extremes i.e. 0%, 0.2% and 0.4% peroxide samples.

Heat profile of 10C/min to 250◦C.

Cool Profile of 10C/min to 30◦C

You can determine the approximate % crystallinity of each compound by taking a ( Hm̊ ) heat of
crystallisation for a theoretical 100% crystalline polypropylene. ( You need to research this.)

Mechanical testing:

Conduct tensile tests on the test bars using an Instron model 5564 tensometer located in lab area
WG33. You need to measure the width and thickness of each sample at its gauge length prior to
each test. This information is fed into the Bluehill software and is used to determine the stress on
the material. Use a crosshead displacement rate of 50 mm/min. Collect the tabulated data from
each batch.

Result: Report the results and their analysis. You will experience hands-on operation of the
processing and characterisation methods. However, because of time limitations in the laboratories
many of the results in raw data format will be given to you.

You have also been given chromatograms of representative of similar CRPP samples ( appended to
this document) – please review these and comment on the data.

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The report:
The coursework report should be minimum of 3000 words ( max to 5000) . Deadline submission date :
by Friday 3rd April 2020, via electronic submission in Canvas.

Your report should include:

 Literature review of the REX processing and of REX to produce CRPP. This is an important
component of the report as reflected by the potential marks to be gained so please spend
your time understanding the technology. In the literature you should cover:
o describe the details of REX processing – what are the intended purpose.
o typical applications of REX
o advantages of this technology over conventional polymerisation technologies.
o control issues with REX processing

 Experimental: description of materials used and quantities, processing equipment and

procedures, process conditions, analytical methods and equipment used. Try to incorporate
a description of the purpose and significance of data from of each experiment in the context
of your REX polypropylene. Include any precautions taken, etc
 Results – present data of any testing or observations made during processing. Present an
analysis of the results and consider any supporting correlations between data from the
different characterisation techniques.
 Discussion : discuss the finding of the results – what do they mean – do they validate/
support/contradict any results from other sources reported in the literature? Suggest
reasons for validation or contradiction. Look at what you can imply from the results in terms
of the REX process used – may be able to use data from two or more characterisation tests
used to support your hypothesis.
 Conclusions – summary of the findings of the study with succinct analysis of the project.
Give a reflective feedback on the usefulness of the project for the development your own
knowledge and skills.
 Recommendations – further work extended research ideas – what could be changed /
improved.
 References – remember to cite these in the body of your report. Sometimes good to refer to
some of these to support your discussions.

Assessment: The report accounts for 50% of the module mark.

REX Processing Rubric

Level: Assessment Rubric Attempt

UoB #: Student Name Level MSc /MEng CPE7009B REX Coursework

Module code CPE7009B Module Title Poly Eng Assigned mark:

Relevance, style and Marks allocated: 30 e d c b a

referencing
Aspect Appraisal % wt 0-19 20-39 40-59 60- 79 80-100
Scope/ Introduction to Shows an appreciation of field of study in 5 Non/ unclear/ Limited without Satisfactorily Detailed, coherent Concise, accurate

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your work/ Aims & context of the module intent with clear Major convincing demonstrates and clearly and well
Objectives definition of study – clarity of objectives deficiencies understanding. nature of the demonstrates articulated
from the work. work. understanding. .

.
Background / justification/ Use of literature to inform understanding
Literature review of REX practices used, through review of Adequate Good background & Focused and well
contemporary and recent practices and 20 Little evidence Limited attempt to evidence of Lit review setting developed
pertinent literature survey/citations. of provide background. background and context for CW. background with
consideration. relevant literature relevant literature.
review.
Spelling , grammar,
presentation, Presentation and articulation of
coherence, expression. arguments with correct spelling and use Major Good use of, well Very good use of,
of grammar. 5 deficiencies in Some deficiencies in Demonstrates structured, logical excellent
majority of a few of these areas. acceptable presentation. organisation and
these areas. grammar and structure.
presentation.
Comments

Constructed knowledge Marks allocated: 65 e d c b a

Aspect Appraisal % 0-19 20-39 40-59 60- 79 80-100
wt
Experimental description and Shows knowledge and appreciation 10 No, or poor, Presented without Satisfactory with Good, accurate Thorough, insightful
application of methodology of engineering/ scientific method coverage without justification for limited acceptable coverage with justification of
used, industrial practices, context convincing use. level understanding justification for methods.
of methods in relation to the task: understanding of use.
techniques

Presentation of data 10 Missing, deficient Evident and Comprehensive,

Results data Evident but complete. Evident, accurate with
superficial comprehensive insightful
and accurate. presentation.

Evaluation/ Analysis of data ( Manipulation and analysis of data. 20 Little attempt of Satisfactory but Very good, accurate
and incorporating findings analysis. Some attempt, superficial analysis of Good, complete and innovative
from literature) but incorrect data. and correct analysis.
Articulation of arguments based on 20 No evidence to analysis. Satisfactory, but of analysis. In-depth analysis with
analysis of data and literature consider analysis in limited depth. comprehensive and
Discussion/ synthesis/ review context of work. Limited, stating Good, logical, creative application of
reflection obvious. attempts to literature findings.
include pertinent
literature findings.
10 No, or limited Synopsis of the Satisfactory, but Complete, succinct,
Conclusions Succinct articulation of the study. attempt. findings lacks incomplete. well structured,
focus. Good, complete, logical presentation
logical
presentation.
Comments:

H&S , Sustainability Marks allocated: 5 e d c b a

Aspect Appraisal % 0-19 20-39 40-59 60- 79 80-100
wt
Consideration of Health, Shows knowledge and appreciation 3 No, or poor, Acknowledged but Satisfactory Major H&S issues Comprehensive, and
safety & sustainability. of H&S issues: coverage. limited detail. consideration of covered, correct through
majority of issues remedies considerations.
with limited proposed.
remedies
.
Comprehensive with
2 Satisfactory recommendations
Reflection Articulation of personal learning No attempt. Limited attempt consideration Insightful for enhancing
experience with view of wider to reflect on work. reflection. experience, insight to
application of REX technology. technology.

Comments.

1st Marker –Print Name Signed: Date:

nd
2 Marker/checker: Signed: Date:

External examiner: Signed: Date:

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GPC – method used:

Base Polypropylene JE6100:

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JE6100 Polypropylene + 0.05% peroxide

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JE6100 Polypropylene + 0.1% peroxide

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JE6100 Polypropylene + 0.2% peroxide

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GUIDELINES FOR HANDLING ORGANIC PEROXIDES (9, 14, 19, 23)

Use only the minimum quantity required.

Wear nitrile gloves, eye protection and body protection such as a lab coat or apron.
Conduct procedures inside a chemical fume hood or from behind a protective shield.
Do not return unused peroxides to the container.
Clean up liquid spills up immediately. Keep spills of solid peroxides wet with an appropriate inert solvent (e.g.
water or aliphatic hydrocarbon). Cover the spill with a wet (water) mixture (1:1:1, by weight) of sodium
carbonate, "kitty litter" or vermiculite, and sand. Dispose promptly as hazardous waste. See Armour (35) for
recommended procedures for specific compounds.
Reduce the sensitivity of peroxides to heat and shock by dilution with inert solvents (e.g. aliphatic
hydrocarbons).
Avoid using solutions of peroxides in volatile solvents. Solvent evaporation should be controlled to avoid
dangerous concentration of the peroxide.
Do not allow peroxides to contact iron or compounds of iron, cobalt, or copper, metal oxide salts, acids or bases,
or acetone.
Do not use metal spatulas to handle peroxides.
Do not allow open flames, other sources of heat or sparks, friction, grinding or forms of impact near peroxides.
Do not use glass containers with screw-cap lids or glass stoppers. Use polyethylene containers, screw caps or
stoppers.
Protect from heat and light.
Store peroxides at the lowest possible temperature consistent with their solubility and freezing point.
CAUTION: Do not store liquid or solutions of peroxides at a temperature below that at which the peroxide
freezes or precipitates. Peroxides in this form are extremely shock and heat-sensitive. Refrigerated storage
of peroxides or other flammable chemicals must be ONLY in "Lab-Safe" or explosion-proof units.

See the following reference for more information on handling peroxides:

http://www.bnl.gov/esh/cms/pdf/peroxides.pdf

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