March 9, 2016

Victrex Energy Solutions

Assessing Polymer Performance in

Hot and Sour Oil and Gas Environments

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AUDIOVISUAL

PRESENTATION

Speakers

Dr. Geoff Small

Energy Market Technology Manager

Victrex

Dr. Alexandra Torgersen

Consultant

Alexandra Torgersen Engineering

Overview Predicting Lifetime in Hot and Sour Environments

NORSOK and ISO ‘compliance’ are frequently referred to by polymer suppliers

Goal: demonstrate the current best possible assessment of lifetime in service

and outline the potential pitfalls of using inappropriate data

NORSOK M710 Standard What is it?

Standard written as test protocol – not as “pass / fail” standard

Testing specified for using Arrhenius extrapolations

No specific test temperatures or duration

Open for differences in testing and interpretation of results

Test Setup Challenges

No specific temperatures—need for acceleration

No specified test duration—50% reduction in properties

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0

10

20

30

40

50

0 500 1000 1500 2000 2500

125°C

135°C

145°C

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-40

-30

-20

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0

10

20

30

40

50

0 500 1000 1500 2000 2500

125°C

135°C

145°C

Interpretation Challenges

Arrhenius extrapolation—not an exact science

Are flat lines on a graph a problem or success?

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-40

-30

-20

-10

0

10

20

30

40

50

0 500 1000 1500 2000 2500

125°C

135°C

145°C

Interpretation Challenges

NORSOK M710 Standard

Test protocol for learning about polymers and elastomers

Need sensible input to give sensible results

Always present all results—interpret results based on specific application

Be careful about extrapolations—eventually degradation happens

Summary

Data from Standard Tests

The most common standards are : ISO 23936 Parts 1 & 2 and NORSOK M710 Edition 3

Approach: ageing at three different temperatures to predict max operating temperature for

25 year lifetime or predicting material lifetime at specific operating temperature

‘Compliance’ means testing in line with the standard

None of the test methods are entirely prescriptive leading to varying degrees of data

presented and lack of clarity around the experimental variables

Test Requirements Overview

Standard material data

RGD testing (elastomers only)

Ageing test (most commonly evaluated and discussed)

Test Methods Ageing Overview

Ageing in at least 3 temperatures in sweet or sour environment

Arrhenius-type extrapolation used to predict lifetime if possible

Assumes a single degradation process and a linear change with time

Material Lifetime Estimates ISO Standard

Test Method Observations Taking a Closer Look

Materials do not comply with the standard—the test method used may comply

Ageing tests estimate polymer lifetime at lower service temperatures

The acceptance criteria are used for lifetime estimation—they are not ‘pass’ or ‘fail’ criteria

Volume swell, weight gain or any agreed mechanical property

Most common mechanical properties are tensile strength / modulus

Lifetime then refers to the time taken to the loss of 50% of this property

Hot and Sour Performance Life Prediction: Useful Tool or Misleading Guidance?

Up next—data on VICTREX® PEEK 450G™ polymer or other Victrex polymers

Shows importance of:

Selection of the appropriate properties for measurement

Selection of the most suitable test duration

Other supporting data can be used to augment the data generated in these test protocols

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Experimental Data from

NORSOK M710 (Editions 2 and 3)

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NORSOK M710: Edition 2

Temp:175°C, 195°C & 210°C Sour Gas Content: 2% Durations, 35 days, 24 days and 25 days

Tensile Modulus: VICTREX® PEEK 450G™ Polymer

NORSOK M710: Edition 2 Observations

Strength and modulus data suggests PEEK will have near infinite lifetime

in the 2% NORSOK environment—strain data suggests a much shorter lifetime

Very little change in properties: selection of appropriate temperature and duration?

Report concluded that PEEK has "very" long lifetime up to 220°C in this environment

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NORSOK M710: Edition 3 Temp: 195°C, 210°C & 225°C Sour Gas Content: 10% Time: Up to 105 days

NORSOK M710: Edition 3 Tensile Strain: VICTREX® PEEK 450G™ Polymer

Tested at an additional temperature

Improved correlation at elevated temperatures

This should lead to a better estimate of lifetime

Temp: 195°C, 210°C, 225°C, 240°C Sour Gas Content: 10% Time: Up to 105 days

NORSOK M710: Edition 3 Estimating Lifetime: VICTREX® PEEK 450G™ Polymer

Data set with four temperatures provides better correlations

Significantly reduced lifetime prediction, especially at lower temperatures

Temperature (°C)

220

210

200

190

180

170

160

150

140

130

Three Data Sets

t50 (years)

1.1

2.5

6.1

15.3

40.3

110.4

317.2

958.0

3052.1

10299.2

Four Data Sets

t50 (years)

1.3

2.7

5.8

13.1

30.5

74.0

187.1

494.2

1368.4

3985.5

NORSOK M710: Edition 3 Estimating Lifetime: VICTREX® PEEK 450G™ Polymer

Strain at break significantly more sensitive to ageing—lower life estimate

Tensile modulus data provides unreliable and poor correlations for

thermoplastics

Temperature (°C)

220

210

200

190

180

170

160

150

140

130

Lifetime Tensile Strength t50 (years)

1.1

2.5

6.1

15.3

40.3

110.4

317.2

958.0

3052.1

10299.2

Lifetime Tensile Strain t50 (years)

0.2

0.3

0.4

0.7

1.1

1.7

2.9

4.9

8.5

15.1

Lifetime Tensile Modulus t50 (years)

1

1.0

1.5

2.3

3.7

6.0

10.0

17.1

29.9

53.9

Conditioning Pre-treatment will depend on the type of polymer

Selective use of degradation data

• Correlation of halving duration versus temperature increases from

o 0.80 to 0.93

Temperature (°C) t50 (years) (post 500

hours data) t50 (years) (all data)

240 0.2 0.3

230 0.4 0.6

220 0.7 1.3

210 1.4 2.7

200 2.8 5.8

190 5.7 13.1

180 11.8 30.5

170 25.7 74.0

160 57.6 187.1

150 134.4 494.2

140 326.7 1368.4

130 829.9 3985.5

Test Duration is Important Tensile Modulus: VICTREX® PEEK 450G™ Polymer

Using long-term data is unusual—short-term data is not useful

NORSOK and ISO seen as a ‘task’ and cost to sell to Oil & Gas market

Max duration usually 35 days at lower temperatures—12 days at highest

Short-Term Data Ending Tests Early: VICTREX® PEEK 450G™ Polymer

Early termination has resulted in a significant

over-estimate of lifetime at temperature

Temperature (°C) Lifetime(Long-term

data)

Lifetime(Short-term

data)

220 1 1

210 3 4

200 6 11

190 15 33

180 40 102

170 110 329

160 317 1127

150 958 4089

140 3052 15791

130 10299 65205

Short-Term Data VICTREX® PEEK 450G™ Polymer and Experimental Polymer

500-hour testing clearly does not give the whole picture

Chemical Analysis Molecular Weight: VICTREX® PEEK 450G™ Polymer

Tensile strength may change very little over the course of the experiment

But molecular weight is changing from the beginning of the experiment

Quantum Mechanical Model Moving Towards a Predictive Model

Bond orders and dissociation energies

Thermodynamic driving forces

Transition states

Kinetics

Product 3TS3’

TS_inter

TS 3

Inter

TS 2

Reactant

Product 2

+ H2O

Conclusions Lifetime Predictions

NORSOK M710 Edition 3 and ISO 23936 are excellent standards for assessing the

performance of polymers in aggressive oilfield environments

Must select the most appropriate property parameters for evaluation

Must ensure the most appropriate ageing duration is selected

Our Stance Victrex Leading the Way

Victrex—leading in lifetime assessment of PEEK polymers and beyond

Ask your polymer suppliers for the same level of detail

VICTREX PLC BELIEVES THAT THE INFORMATION CONTAINED IN THIS DOCUMENT IS AN ACCURATE DESCRIPTION OF THE TYPICAL

CHARACTERISTICS AND/OR USES OF THE PRODUCT OR PRODUCTS, BUT IT IS THE CUSTOMER’S RESPONSIBILITY TO THOROUGHLY TEST THE

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