Evolving Needs in Non-Metallic Seats and Seals: New...

Evolving Needs in Non-Metallic Seats and Seals:

New Materials for the Valve Industry

Dr. Tim Bremner

Vice President of Materials Technology

Hoerbiger Corporation of America, Inc.

&

Co-Director - APPEAL Industrial Research Consortium

& TEES Research Engineer

Texas A&M University

Outline

1. Material Families of Interest

2. Technical Demands – Future Targets

3. Rethinking Qualification

Exposure Testing

Upper Service Temperatures

Defining Service Environment

4. Concluding Remarks

Material Families of Interest

Material Families of Interest

Not talking about FKMs, FFKMs, NBRs or HNBRs

Predominantly thermoplastics with properties above nylon

High modulus, low creep, high chemical resistance, non-existent RGD

failure

Being asked to provide single solutions for operation at -40 °F to 600 °F

Hotter, longer life, more corrosive, broader range of application, “one size

fits all”

PAEK family, PPS, PBI, polyimides

High Performance Polymers

- Invented by the Egyptians

Current State of High Performance Non-Metallics

Technical demand and application space for new materials is outpacing

the rate of commercialization of viable products

Demand for non-metallic solutions is growing or accelerating in most

market sectors which utilize non-commodity materials

Engineering risk is (arguably) higher today than it has ever been whereby

materials are placed into applications without basic understanding of the

long term or service condition performance

Standards and qualification criteria are weak or absent in critical service or

environmentally risk prone arenas

Fundamental science and engineering is not being conducted at a scale or

with the focus that is required to mitigate these risks and gaps

Why an Increased Demand?

Shale Gas

Offshore,

Ultra-Deep Tight gas,

high H2S

Heavy Oils

Economics - Demand for Engineering Polymers? (Do the materials’ guys have job security?)

2011 US annual market for (currently at HCA processed) HPPs in Oil & Gas Industry. Market size: Sold resin in m lbs and m USD with 2011 material prices.

2011 Global annual market for HPPs in all industries. Market size: Sold resin in m lbs and m USD with 2007 material prices.

Global Market: 1,363m lbs (~8,799m USD, at 2007 resin prices)

Industrial Application*: 173m lbs (~1,712m USD, at 2007 resin prices)

35%

30%

17%

18%

North America

Europe

Japan

China, ASEAN, Rest

20%

29%

18%

13%

12%

7%

Industrial

Electrical and Electronics

Automotive

Others

Aerospace and Defense

Medical

* Industry accounts for 20% of market volume but 30% of market value

Long Term: All Engineering Polymers in Energy Sector globally.

119 million lbs $1.252 Billion USD CAGR 9.9%

Short Term: Certain HPP's in Oil & Gas Industry within the US:

24m lbs $451 Million USD CAGR 9.2%-11.2% Price per lb higher in Oil &

Gas Sector

39%

30%

31%Energy Sector: Oil & Gas

Energy Sector: Other

Other Industrial

Industrial Application: 61m lbs

The Demands for Engineered Materials Will Rise The move to hotter and more chemically aggressive environments will continue to

increase

“World Offshore Drilling Spend Forecast 2009-2013”, EnergyFiles & Douglas-Westwood

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Shallow Water Deep Water

Subsea Systems Exploration in offshore reserves will continue to increase

More environmentally sensitive areas = more stringent regulation and higher performance & increased lifetime requirements

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Global Subsea Production Capex ($MM)

# of Subsea Trees Onstream

Km of Subsea Production Umbillicals Installed

The “Average” Materials Engineer / Scientist in O&G

Consider:

>90% of sealing applications in today’s O&G environment utilize an

elastomer or nothing more glamorous than a nylon

Individuals employed as “Materials Engineers” in engineering and operating

companies are, in the oil and gas arena, metallurgists or well versed in

elastomers

infrequently need to consider high temperature thermoplastics; this is

changing

High performance thermoplastics as we define them today are still new and

not well understood

What Is the Industry Asking For?

Guidance on material selection / differentiation at service condition

Polymers are sold or specified by batch properties and rarely chemical

structures; yet, the chemistry and physics is structurally dependent.

e.g. unraveling PAEK polymerization technology platforms:

Solvay (Gharda) electrophilic – PEEK, PEK, PEKK

Solvay nucleophilic process - Ketaspire – PEEK, PEKEK, PEKK

Gharda - Gatone PEK’s

Victrex nucleophilic process – PEEK, PEK, PEKEKK

Oxford Performance Materials - PEKK

Evonik (Degussa) – PEEK

Polymics – new PAEK product platform

What Is the Industry Asking For?

Property and dimensional retention at service condition

The polymer industry tests under ASTM, ISO, and other standard methods

Often (usually) room temperature and pressure, or at some other “typical”

condition

This type of data has been utilized for:

material / vendor selection

engineering standards development in your companies

material specifications for specific parts in specific service

vendor selection

This is not good engineering practice

“It’s all we have to go on” is no longer acceptable

Common Themes – What Is the Industry Asking For?

The high performing materials of yesteryear are getting closer to the edge

of their performance limits

in many cases, PEEK users had a material that exceeded the performance

demands of the application

this situation is declining as the demands increase and serviced markets

broaden into unexplored territory

The responses include:

more rigorous/detailed specification

more monitoring of conformance

identify and control sources of variability

optimize processes

The Value Chain

Polymerization

In Reactor

Reinforce /

modify:

Fillers, fibers,

etc.

Primary

Polymer

Structures

Machine /

assemble

/ finish

Melt

Conversion:

Stock /

finished shape

Application

@ End User

Makes a polymer

Delivers a compound

Molds a shape

Machines / assembles

Expects it to last as

long as predicted,

and work the same

every time

It is uncommon that these contributing agencies will ever get together and discuss

the engineering specifics of the service environment, performance expectations,

true technical capabilities of their company, or true costs.

The end-user takes (much)

of the risk.

Service Conditions -

Future Targets

Operating Regimes: HPHT

UK Energy Institute Model Code of Safe Practice (Part 17)

High temperature defined as undisturbed bottom hole temperature > 300 °F

High pressure is defined using maximum pore pressure of any porous formation

with hydrostatic gradient in excess of 0.18 bar/m (0.8 psi/ft)

OR

“A formation requiring deployment of pressure control equipment with a rated

working pressure in excess of 690 bar / 69 Mpa / 10,000 psi”

17

Operating Regimes: HPHT and Beyond

Today we don’t have non-metallics that will operate across these regimes

Materials alone will not solve the ultimate problem; changes in design basis

to accommodate material features are required

What about steam? - We’re being asked for 600 deg °F steam service at

14,000 psi, unbuffered.

Autumn 2008 Oilfield Review, Schlumberger Vol 20(3)

Operating Regimes

Location Temperature Range

(existing or anticipated)

Pressure Range

(existing or anticipated)

Surface Operations 175 °F – 275 °F (80 °C – 135 °C)

200 – 5,000 psi (14 – 345 bar)

Subsea Equipment -50 °F – 375 °F (-45 °C – 190 °C)

10 kpsi (shallow) (690 bar)

15 – 20 kpsi deep (1.4 kbar)

up to 27 kpsi (1.9 kbar)

Down Hole – Land Based 175 °F – 275 °F (80 °C – 135 °C)

200 – 5,000 psi (14 – 345 bar)

Down Hole - Subsea -50 °F – 500 °F (-45 °C – 260 °C)

15 kpsi @ > 450 °F

40 kpsi @ > 450 °F (2,700 kbar @ > 230 °C)

Steam – Direct Injection -50 °F – 550 °F (-45 °C – 288 °C)

In order to focus materials development programs, need to focus / sub-

categorize

Another way to look at it…

Rethinking Qualification – Lifetime Prediction

Lifetime Prediction

Today’s scientifically substantiated prediction of lifetime of non-metallic

components in critical service environments is mediocre at best

Duration of

Exposure Test

Lifetime Prediction

Today’s scientifically substantiated prediction of lifetime of non-metallic

components in critical service environments is mediocre at best

Today, we assume that:

1. Extrapolation works

2. A simple monotonic function describes the deterioration of some

measurable physical property over the entire predicted service life of the

material

3. We are measuring a material property during exposure testing that is

reflective of the critical performance attribute of the part in service

ie. does it make sense to measure tensile strength for a ball valve seat

material?

4. A constant chemical / physical environment will exist for the life of the part

in service

Lifetime Prediction

The approach is directly analogous to work conducted on polyolefins in the

70’s and 80’s

material balance at molecular level for dominant degradation pathways

concentration dependent changes in reaction mechanism / profile

physical effect or chemical effect or (likely) both

Resulting in:

replacement of strongly reacting species

inhibition of reaction pathways with small molecule additives or polymer

bound functionality

reduced rate of polymer degradation

more accurate prediction of lifetime

“specialized” testing becomes standard

Rethinking Qualification – Upper Service Temperatures


Q: What is the maximum temperature that this polymer can be exposed to

without failing?

A: It depends (ie. UL 746B doesn’t cut it…)

Time dependence – how long is the exposure?

Environment – gases, fluids, other contact

Configuration dependence – what is the part configuration in service?

forces, pressures

The value of a Product Data Sheet from typical material provider ranges

from “mildly useful” to “misleadingly dangerous”


Consider: Two different applications, same material

1. Packing ring in reciprocating compressor packing

case

no close conforming metallic structure to retain

ring shape

forces are compressive on the OD (gas pressure),

shear with rod motion

maximum design temperature = 320 °F (160 °C)

2. Ball valve seat

constrained and supported in seat groove

forces are compressive (mainly) with some shear

hot process fluids (xylene, styrene monomer)

maximum design temperature = 440 °F (226 °C)


The old way:

“Pick a temperature you’re comfortable with and reduce it by 50 °F, just in

case”

With better tools and advancements in modeling* of non-metallics (the

visco-elastic problem) we can and should be more precise when defining

suitability of material for a particular device or component as a function of

temperature

* we still need to validate the models with real hardware

Rethinking Qualification - Defining Service Environment

Defining Service Environment - By Example

PBI (polybenzimidizole) from Celanese known as Celazole®

very high glass transition temperature = 801 °F (427 °C)

heat distortion temperatures at 815 °F

on own, not tough enough to be used in corrosive / rough service

Showed promise in blend systems for engineering applications

commercially as TU-60, TL-60, TF-60, U-60

Composition Heat Distortion Temperature @

1.8 Mpa Load

Homopolymer PBI 815 °F

50/50 PBI/PEEK Blend 590 °F

Compare: Unfilled PEEK 315 °F

50/50 PBI / PEEK Blend + Carbon Fiber 608 °F

Compare: Unfilled PEEK + Carbon Fiber 530 °F

Defining Service Environment – Field Experience

Material from Molding Company A ≠ Molding Company B

complex, still not well understood, blending and molding process

Performance in moisture or steam

some good, some bad, some catastrophic

in steam, unsupported rings / seals crumble

Performance in high temperature chemical processes

very mixed reviews; failures at weak points in part design

Outcome

Reputation suffers

Lack of confidence by Application Engineers

From limited acceptance to outright rejection

A “failed” introduction due to inadequate understanding of wh

Defining Service Environment – Field Experience

From an earlier slide:

Technical demand and application space for new materials is outpacing the

rate of commercialization of viable products

Fundamental science and engineering is not being conducted at a scale or

with the focus that is required to mitigate these risks and gaps in knowledge

This is one example (there are others) of a material being pushed (or

pulled?) into an application where insufficient technical justification

existed to support its use

Concluding Remarks

High

Performanc

e

Elastomers

By analogy:

Polyolefins (PE, PS, PP) and nylons used to be new / novel and advanced

materials

Engineering Polymers - Evolution

•Reactor design

•Catalyst technologies

•Limits of technology force

product into some

application space

•Post reactor modifications

•Reactive extrusion, grafting,

copolymerization, blends / alloys /

functionalization

•Novel conversion methods

•Increased complexity in meeting

application demands

Ra

te o

f N

ew

Ap

plic

atio

ns S

erv

ice

d

Time

•Complex solutions become

cumbersome

•Technical demand increases

•Inventions of better polymers

reach commercial reality

•High end polymers become

commodity, and new families

emerge

High

Performanc

e

Elastomers

Where are we today?

Engineering Polymers - Evolution

•Reactor design

•Catalyst technologies

•Limits of technology force

product into some

application space

•Post reactor modifications

•Reactive extrusion, grafting,

copolymerization, blends / alloys /

functionalization

•Novel conversion methods

•Increased complexity in meeting

application demands

Ra

te o

f N

ew

Ap

plic

atio

ns S

erv

ice

d

Time

•Complex solutions become

cumbersome

•Technical demand increases

•Inventions of better polymers

reach commercial reality

•Engineering polymers become

commodity, and new families

emerge

Aromatic polyethers /

ketones / imides / azoles

Thermosets (!)

I think we’re about here

New Materials There are few new polymers today that I would consider to be “breakthrough” technologies

Instead, expansion of the application envelope and markets with

blend systems

utilizing two polymers in place of one to “tune” desired attributes in property

balance

in the infancy of many decades of work

post reactor chemical modification

crosslinking, grafting

hydrophobicity, hydrophillicity

wear chemistry modifiers (sulphonation)

processing technologies

shear modifying entangled polymers to give higher ductility

better thermal control during molding (esp. large cross sections)

injection vs compression vs extrusion

none is “better” across the board, they are just different

New Materials – High Temp, Hi P, Low Wear

Evaluating new blends of higher melting / higher modulus PAEK’s, PBI’s,

PI’s and their blends

Material Type Flexural Modulus (kpsi) Tg (°F) Tm (°F)

Traditional PEEK 594 289 644

PEK 595 315 705

PEKK 660 320 680

PEKEKK 623 338 732

PEEK/PBI 943 801 n.a.

PEEKK 651 334 698

PEDEKK 865 408 831

Polyimide – P84NT type 545 698 n.a.

Polyamideimide (Torlon) 1110 534 n.a.

What Is Occurring in Fundamental Research?

Some “recycling”

significant interest in (for example) revisiting the fundamentals of PPS

processing, blending, reinforcing beyond the traditional

a good price/performance proposition

novel blends, reactive processing and functionalization

More is being done at the fundamental level of materials science to

understand the “why” in material performance

If we can understand more of the “why”, we increase our potential to

manipulate the performance attributes of the material during part forming,

thermal processing or even at polymerization

More industry / university collaborations (in various forms) are occurring

good return on investment, multiple benefits

opportunity to lead the effort rather than accept the outcomes of others

perceptions of “need”

The Value Chain

Polymerization

In Reactor

Reinforce /

modify:

Fillers, fibers,

etc.

Primary

Polymer

Structures

Machine /

assemble

/ finish

Melt

Conversion:

Stock /

finished shape

Application

@ End User

Makes a polymer

Delivers a compound

Molds a shape

Machines / assembles

Expects it to last as

long as predicted,

and work the same

every time

It is uncommon that these contributing agencies will ever get together and discuss

the engineering specifics of the service environment, performance expectations,

true technical capabilities of their company, or true costs.

The end-user takes (much)

of the risk.

Application

Engineering /

End Users

Acknowledgements

Hoerbiger Corporation of America, Inc.

Dr. Lin Jin

Teresa Martinez

Thomas Willis

Barton Scarbrough

Texas A&M University

APPEAL Research Consortium

Cameron

Ron Manson

Thank You for the Opportunity!

Evolving Needs in Non-Metallic Seats and Seals: New...

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