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Plastics and elastomers in corrosive environments Dr Karin Jacobson Research Leader Polymeric Materials Swerea KIMAB AB, [email protected]

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Page 1: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Plastics and elastomers in corrosive environments

Dr Karin Jacobson

Research LeaderPolymeric MaterialsSwerea KIMAB AB, [email protected]

Page 2: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Swerea = Swedish researchCollection of Swedish material research

institutes in one group

Some of the work presented here dates back to when we were the

Swedish Corrosion Institute

Gunnar Bergman started the work on polymers corrosion in 1981

Page 3: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Our expertise – Need driven industrial research • Member program: Polymeric Materials in Corrosive Environments • Approximately 50 members• From producers to end users • Main focus areas are chlorine production, sulphuric acid, flue gas cleaning and

pulp and paper production• We are also active in a number of research projects and do contract work,

material recommendations, ageing studies and exposures in harsh environments (H2SO4, HF, ClO2, spent acid, chlorine….)

Page 4: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Storage tanks for hydrochloric acid made of FRP (fi ber reinforced ester plastic)

Service life?

Page 5: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Page 6: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Page 7: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Stress corrosion failure in FRPlined with PVDF

Page 8: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

600 m3

hot pulp

Page 9: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Filament-wound fiber

Page 10: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

5 years in service, Brine with Cl2

Page 11: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Diffusion

• Major problem, especially for fluoroplastics• Lack of data• Sorption/desorption often tedious and time-

consuming if at all applicable• Developing quick and easy to use techniques to

generate data

08/08/2014

Page 12: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Indicator technique for measuring diffusion

08/08/2014

Pieces cut from material to be studied

Exposed inselected mediaat chosentemperature

Films exposedin suitable indicatorsolution

Thin film cutfrom cross-section

2 cm

Page 13: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

x

∆∆∆∆xt

= 2D

t = time of immersion in acid(here 24 hours)

Page 14: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

The Einstein equation

Dx

t= 2D

∆∆∆∆xt

= 2D

Page 15: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

ClO2 2.2.10-7

HCl 2.0 .10-7

HNO3 1.2.10-7

HBr 1.4 .10-9

H2SO4 4.0.10-10

08/08/2014

Increasing diffusion rate

Pure water is the fastest

Diffusion coefficients in PVDF at 80 °C

Page 16: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Sample from the rubber lining, liquid phase

08/08/2014

0.3 mm

1.3 mm

3.1 mm

Page 17: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

An indicator technique was used to visualise the diffusion front

08/08/2014

Butyl rubber

NR

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08/08/2014

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Page 19: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Corrosion approach• Industry prefers similar approach independent of

material (steel or polymer)• Facilitates design and life-time prediction

Corroded stainless steel pipe Corroded FRP pipe

Page 20: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Chemical resistance data

Page 21: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

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90°C moist Cl 2from the cells

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08/08/2014

Corrosion rate = 0.3 mm/√year

Diffusion rate = 1.3 mm/√year

Page 23: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Chemical resistance polypropylene, S = satisfactory, L = limited, NS = not suitable

Chemical Concentration 20°C 60°C 100°C

Nitric acid Up to 30 % S NS NS

Nitric acid From 40 to 50 % L NS NS

Nitric acid Fuming NS NS NS

Pickling in mixed acid 20% HNO3, 4% HF ca 65°C

Page 24: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Crack propagation in polyethylene

Page 25: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Problem with weldability during repair work

08/08/2014

Tried to weld here but failed.

More material had to be removed.

Page 26: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

About 14-15 mm

The wall thickness is 40 mm

Page 27: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Leaking welds that could not be repaired

08/08/2014

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08/08/2014

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08/08/2014

A decision is made to not use PP i HCl environments

Page 30: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Influence of processing technique on material performance

08/08/2014

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08/08/2014

The two parts are from different producers

The plant has now stopped buying from the supplier of the flange due to this problem

Corrosion in mixed acid (HF and HNO3)

Page 32: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Injection moulded parts

Extruded pipe

All parts from the same supplier

Page 33: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Injection moulded bend Extruded pipe

100 µm

Microscope with polarised light to study crystal structure

Page 34: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Sorption and desorption

Viton rubber before and after exposure at a paper m ill

Page 35: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Crackedsurfaceof an FRP -chimney

Page 36: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

08/08/2014

Absorption anddesorption of water

Page 37: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

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Problems due to thermal elongation/contraction

A leak in a PP pipe with external reinforcement of FRP for 90°C NaOH

Page 38: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Institut de la Corrosion – S:t Etienne

Experts on testing in H2S

Page 39: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Polymeric materials in nuclear- and water power plants

This image cannot currently be displayed.

Assessing the status of polymeric materials in our nuclear and water power plants

Page 40: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

� Study of polymeric materials in concrete constructi ons

� We have visited 7 of the 10 reactors in Sweden

� Forsmark 2

� Oskarshamn 1, 2 och 3

� Ringhals 1, 2 och 3

� Identifying polymeric materials with need for further investigations

� Investigating the knowledge about polymeric materials

� Identifying differences between different plants

� Main focus 2014 on elastic seals and PVC strips

Page 41: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

RecyclingTunnel kiln lime in EPDM

• Major bi-product from steel production• Similar properties to CaCO3

• Performing ageing study

Co-operation between Swerea,Höganäs and Gislaved

Page 42: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Concluding remarks• Lack of relevant data and standardised material often

makes the use of polymeric materials in harsh environments to be full scale experiments

• The corrosion approach helps the end users to predict service life of their equipment

• Our research focuses on the generation of relevant data so that we can help the end users with material choices, status determinations and failure analyses.

Page 43: Plastics and elastomers in corrosive environments - SGF · Plastics and elastomers in corrosive environments ... Polymeric materials in nuclear- and water power plants ... Study of

Thank you!