How do bimodal polyethylene resins provide

improved pipe properties?

Sebastian Joseph, Ph.D.

October 31, 2005

Lyondell Chemical Company - Overview

Lyondell is one of the worlds largest chemical companies, with

$15.9 billion in assets.
Lyondell companies include:

Three wholly owned businesses Lyondell, Equistar and

Millennium
LYONDELL-CITGO Refining (LCR) joint venture

Lyondell is a major global manufacturer of ethylene, propylene,

titanium dioxide, styrene, polyethylene, propylene oxide and acetyls.
Lyondell is headquartered in Houston, TX, operates on five
continents and employs nearly 10,000 people worldwide.
Lyondells consolidated pro forma 2004 revenues were $15.2 billion.

Advantages of new generation bimodal

polyethylene pipes

Improved mechanical properties

Increased pressure rating

Resistance to slow crack growth (SCG)
Resistance to rapid crack propagation (RCP)

Increased service pressure

Reduced wall thickness
Increased capacity

Todays discussion

Describe unique features of bimodal polyethylene that

allow step-out performance in pressure rating, stress
crack resistance and rapid crack propagation of
polyethylene pipe

Outline

Evolution of polyethylene pipe performance

Factors affecting service life of polyethylene pipe
SCG resistance unimodal vs. bimodal
RCP resistance
Summary

Hydroststic Design Stress (Water), psi

Evolution of polyethylene pipe performance

1200

1000
800
600
400
200
0
PE1404

PE2406

PE3408

PE4710

Polyethylene Pipe Code

* With the implementation of increased design factor

Properties controlled by resin producers

Molecular weight

Polymer is made up of multiple repeating units of a monomer.

nCH2=CH2

-(CH2-CH2)-n

MW =28

MW = 1,000 1,000,000

Molecular weight distribution (MWD)

Polymers are composed of chains of differing lengths, which results in a

distribution of molecular weights.

Density

Incorporation of comonomer (butene, hexene, octene) in the polymer

chain lowers density (crystallinity) and leads to short chain branching.
C
C
-C-C-C-C-C-C-C-C-C-C-C-

Butene Branch

Unimodal and bimodal polyethylenes

Weight fraction

Molecular weight

Bimodal molecular weight distribution

Weight fraction

Unimodal molecular weight distribution

Molecular weight

Bimodal polyethylenes are characterized by two peaks in the molecular

weight distribution.

Factors affecting polyethylene pipe service life

Knee

Hoop Stress

Stage I

Stage II

Field experience confirms that

pipes predominantly fail due to
slow crack growth (Stage II) as
compared to bursting (Stage I).
Pipe service life is determined by
resistance to slow crack growth.
Other factors include:

Failure Time

Environmental
Loading

SCG Resistance

Pipe Service Life

Conventional property balance with unimodal PE

SCG Resistance

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Hydrostatic Design Stress

Constraints on unimodal PEs

High SCG resistance requires low densities
Low densities result in low HDS

Density

Density

SCG resistance of unimodal and bimodal PE grades

Literature* shows that for unimodal PE grades, SCG resistance

increases with

Increase in molecular weight

Decrease in density
Type of comonomer (for unimodal grades)

*Berthold, J. et al., Plast. Rub. Comp. Proc. Applcn., vol. 25, 368(1996)

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3 Ps of polymer design*
Polymer (Density, MI)

Processing

(Resin Manufacturer)

(Extrusion at Pipe Manufacturer)

HDS
Pressure Rating

Properties
(Utility/
Municipality)

* Wallace Yau, Lyondell

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SCG
Slow Crack
Growth

RCP
Rapid Crack
Propagation

SCG resistance of unimodal and bimodal PE grades

Literature* shows that for unimodal PE grades, SCG resistance

increases with

Increase in molecular weight

Decrease in density
Type of comonomer (for unimodal grades)

Bimodal PE grades at a higher density show an order of magnitude

increase in SCG resistance over unimodal grades

For example, a bimodal grade at 0.948 density showed failure

times > 1000 hours, while a unimodal PE grade at 0.940 density
and equivalent molecular weight had failure times of ~100 hours

*Berthold, J. et al., Plast. Rub. Comp. Proc. Applcn., vol. 25, 368(1996)

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Structure of unimodal PE resins*

Most of the comonomer

is found in the low
molecular weight
fraction, which
contributes very little to
SCG resistance.
High molecular weight
fraction has about six
orders of magnitude
higher SCG resistance
than low molecular
weight fraction.

10000

7
Short Chains/1000 C

1000

6
5

100

4
10

3
2

PENT Failure time, hours

Key Findings:

1
0

0.1
0.1 - 3

3-8

8 - 15

15 - 41 41 - 400

67% of distribution
33% of distribution
Molecular weight range (104)

* Graph generated from Tables I and II in Lu, X. et al, J. Poly. Sci., Part B: Polym. Phys., vol. 34, 1809 (1996)
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Optimum structure for PE pipe resin*

Place comonomer in the high MW portion of the distribution and no

comonomer in low molecular weight portion of the distribution.

Difficult to implement with traditional catalyst systems in a single

reactor

Most of the comonomer is placed in the low MW fraction.

Weight fraction

Comonomer distribution in unimodal resins

Comonomer
Distribution

Molecular weight

* Brown, N. et al, Plast. Rub. Comp. Proc. Applcn., vol. 17, No. 4, 255 (1992)
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Multi-reactor approach to bimodal PE

Independent reactor control

Molecular weight
Density
Novel catalyst technology

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Polymer property control

Molecular weight
Molecular weight distribution
Comonomer distribution
Density

How do bimodal PE resins provide improved pipe

properties?

Preferred location of comonomer

Higher crystallinity (density) over unimodal resins at same level of SCB

Leads to higher hydrostatic design stress

Eliminates constraints imposed by unimodal PE resins

Increase in molecular weight without sacrificing processability

Weight fraction

Comonomer distribution in bimodal resins

Comonomer
Distribution

Molecular weight

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Property balance with unimodal and bimodal PE

SCG Resistance

Pipe Service Life

Bimodal PE

Unimodal PE
SCG Resistance

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Hydrostatic Design Stress

Bimodal PEs remove constraints

High SCG resistance at high densities
High densities result in high HDS

Density

Density

How about rapid crack propagation (RCP)?

RCP refers to the propagation of an impact event over several lengths of

a pipe.
Resistance to RCP is characterized by ISO 13478 (small scale steadystate or S4 test).

Tc , which refers to temperatures at a given pressure (5 bar), above

which RCP will not occur.

North America is currently in process of implementing RCP into ASTM

D2513.
Pc and Tc, in addition to inherent resin impact resistance, also depends
on pipe diameter and thickness.

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Pc , which refers to pressure at a given temperature (usually 0 oC),

below which RCP will not occur.

Not solely a resin property

How is RCP affected by PE molecular structure?

Clutton et al* showed that Tc from the RCP test was directly correlated with
Td-b, the ductile-brittle transition temperature from the Charpy test
Molecular weight has a significant effect on Td-b.

An increase in molecular weight reduces the temperature at which RCP

can occur

Trade-off between RCP and SCG

Homopolymer PE, which has poor SCG, is predicted to have the highest
resistance to RCP!

RCP resistance of bimodal PE is obtained by tailoring the molecular weight

and distribution

Pipe processability is not impaired by an increase in molecular weight

for bimodal PE resins

*Clutton, E.Q. et al., Plast. Rub. Comp. Proc. Applcn., vol. 27, 478(1998)
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Summary

Step change performance of bimodal polyethylene pipe

resin is a result of tailoring the polymer structure to
achieve:

Appropriate placement of comonomer for SCG

resistance

Tailoring the molecular weight and distribution for

RCP resistance

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Questions?
Bimodal polyethylene
Sebastian Joseph
sebastian.joseph@equistar.com
Bimodal polyethylene pipe processing
Adel Haddad
adel.haddad@equistar.com
Ideas for webinar improvement
Bill Podborny
william.podborny@equistar.com

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