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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
Page 2
Material Families of Interest
Page 3
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
Page 4
Page 5
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
Page 6
Page 7
Why an Increased Demand?
Shale Gas
Offshore,
Ultra-Deep Tight gas,
high H2S
Heavy Oils
Page 8
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 $451 Million USD CAGR 9.2%-11.2% Price per lb higher in Oil &
Gas Sector
39%
30%
31%Energy Sector: Oil & Gas
Energy Sector: Other
Other Industrial
Industrial Application: 61m lbs
Page 9
The Demands for Engineered Materials Will Rise The move to hotter and more chemically aggressive environments will continue to
increase
“World Offshore Drilling Spend Forecast 2009-2013”, EnergyFiles & Douglas-Westwood
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illio
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Capex
Shallow Water Deep Water
Page 10
Subsea Systems Exploration in offshore reserves will continue to increase
More environmentally sensitive areas = more stringent regulation and higher performance & increased lifetime requirements
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# o
f Su
bs
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Tre
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Global Subsea Production Capex ($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
Page 11
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
Page 12
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
Page 13
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
Page 14
The Value Chain
Page 15
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
Page 16
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
Page 18
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)
Page 19
In order to focus materials development programs, need to focus / sub-
categorize
Another way to look at it…
Rethinking Qualification – Lifetime Prediction
Page 20
Lifetime Prediction
Today’s scientifically substantiated prediction of lifetime of non-metallic
components in critical service environments is mediocre at best
Page 21
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
Page 22
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
Page 23
Rethinking Qualification – Upper Service Temperatures
Page 24
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”
Page 25
Upper Service Temperatures
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)
Page 26
Upper Service Temperatures
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
Page 27
Rethinking Qualification - Defining Service Environment
Page 28
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
Page 29
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
Page 30
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
Page 31
Page 32
Concluding Remarks
High
Performanc
e
Elastomers
Page 33
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
Page 34
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
Page 35
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
Page 36
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”
Page 37
The Value Chain
Page 38
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
Page 39
Thank You for the Opportunity!
Page 40