International Association for the

Properties of Water and Steam

IAPWS and IAPWS Cycle Chemistry

Technical Guidance Documents
Barry Dooley
IAPWS Executive Secretary
IAPWS TGD Chair

Australasian Boiler and HRSG Users Group (ABHUG)

Brisbane, Australia
30th October – 1st November 2019
 IAPWS Objectives

The objectives of the Association are to

advance the knowledge of the properties of
water, steam and aqueous systems,
particularly those properties and guidance of
industrial importance, and to make the
knowledge freely available to engineers and
scientists the world over.
 The Members of IAPWS
Countries or neighbouring countries
• Members
Australia BIAPWS [Britain and Ireland]
Canada Czech Republic
Germany Japan
New Zealand Russia
USA
Scandinavia [Denmark, Finland, Norway, Sweden]

• Associate Members
Argentina and Brazil China
Egypt France
Greece India (New 0919)
Italy Switzerland

(under formation: Israel, and The Netherlands & Belgium)

 IAPWS Working Groups (WG)
(meet every year to conduct the IAPWS work & business
with work continuing through the year by Task Groups)

• Thermophysical Properties of Water and

Steam, TPWS
- Established IAPWS area (1929) – Steam Tables
• Industrial Requirements and Solutions, IRS
- Steam turbine manufacturers worldwide are members
• Subcommittee on Seawater, SCSW
- Formed in 2008/2009 to address global seawater needs
• Physical Chemistry of Aqueous Solutions, PCAS
- Formed in 1990 to support power plant chemistry
• Power Cycle Chemistry, PCC
- Technical Guidance Documents for all Generating Sources

Details of each WG are on website (www.IAPWS.org)

 IAPWS International Penetration
IAPWS IF-97
and the Steam
Tables around
the World

The basis
of every
power
plant
worldwide
 International Association for the
Properties of Water and Steam

New IAPWS Guidance

for
Fossil, Combined Cycle /HRSG
and Industrial Plants
 New. Technical Guidance Documents
Since AHUG 2018

• Air In-Leakage (AIL) – published early 2019

• Chemistry Management in Generator Water Cooling

during Operation and Shutdown – September 2019

• FFS for Industrial Plants – September 2019

• Revision - FFS for Fossil. Combined Cycle and Biomass

Plants – September 2019

• Corrosion Products in Flexible, Cycling and Two-

shifting Plants – White Paper – September 2019
 New. Technical Guidance Documents
TGD9-18. Air In-Leakage (AIL)

• Importance of AIL in Performance and Cycle Chemistry

• Locating and Measuring AIL
- Chemistry – Dissolved Oxygen and CACE
- Vacuum Fall Test, He Tracer Method, Smoke
• Detailed Science behind AIL
• Five Base Cases as for other IAPWS TGD
• AIL Program/Plant Team
• Customizations
- Different cycle chemistries - detailed tables for O2 and CACE
- Challenges with Air-cooled Condensers
- Challenges for plants with Heller Towers and Jet Condensers
- Effects of Pollution
 TGD - Air In-leakage (AIL)

• Very common problem where oxygen exceeds

IAPWS limit at CPD of > 10 ppb
• Affects cycle chemistry and plant productivity
- Reduces shell side film heat transfer
- Affect levels of oxygen and CO2
• AIL makes chemistry control non-optimum
• Important for all-ferrous and mixed-metallurgy
• Impact on cycle chemistry (oxygen and CACE)
• Need condenser system to be leak tight
• Back pressure increases with high AIL
 Effect of AIL on Chemistry Treatments
(For example with CPD Oxygen > 10 ppb)

• AVT(R)
- Cannot maintain AVT(R)
- Increased copper alloy corrosion
- *Reducing agent cannot overcome AIL*
• AVT(O)
- No reducing agent used
- Control of boiler/evaporator oxygen
- Cannot maintain optimum AVT(O) with minimum Fe
• OT
- Cannot maintain optimum OT
- Operation for DA and Heater Vents
- Minimize Fe
• FFS
- Same constraints as other treatments
 Detection & Measurement of AIL

• Instrument-based Methods
- Vacuum in condenser
- Vacuum fall test
• Online Cycle Chemistry vs. AIL
- CACE at CPD, boiler water, steam
- Oxygen at CPD
• Tracer-based Methods (Helium)
• Smoke Detection
• Acoustic Testing
• IR Surveys
• Shaving cream
 Air In-leakage (AIL) – Detection
Vacuum Fall / Drop / Decay Test

Decay of vacuum in condenser

when vacuum pumps turned off

mL is leak rate of air in g

s is time in seconds
A is normal leak rate
B Leak rate is too high
 Guidance for AIL Control & Supervision

• Plant Management Buy-in (need for AIL control)

• AIL Team:
• Unit Operators
• Plant Chemists
• Plant Engineer/Performance Team
• Inspection Services/Maintenance Dept.

• Identification of excursion as AIL

• Isolation of AIL location
• Repair
• Test
 Technical Guidance Documents

Feedwater Corrosion Products (#1 Problem)

TGD6-13(2014) - Significant Advancement Worldwide

Suitable methods
• Post sample digestion UV-Vis (Ferrozine) with
a 5 cm cell - Fe only
• Graphite Furnace Atomic Absorption spectrometry (GF-AA) post
sample digestion
• Inductively coupled plasma mass spectrometry (ICP-MS) post
sample digestion

Key points are:

1. Full digestion for all samples required
2. Detection limit of < 2 μg/kg required
(lower the DL the better)
 Achievable Total Fe & Cu Levels –
Different Plant Types/Optimized Chemistry
Feedwater
OT: Total Fe = < 1 μg/kg
AVT: Total Fe = < 2 μg/kg
AVT (Mixed): Total Fe & Cu = < 2 μg/kg
HP/LP Heater Drains: Total Fe & Cu = < 10 μg/kg
CCGT Evaporators/Drums
AVT/PT/CT: Total Fe = < 5 μg/kg
Air-Cooled Condenser (ACC)
ACC Outlet: Total Fe = < 10 μg/kg
Post Condensate Filter: Total Fe = < 5 μg/kg
Cogeneration Plants
Condensate Return: Total Fe = < 10 μg/kg

15
 Technical Guidance Documents

But Monitoring Corrosion Products in Flexible,

Cycling and Two-shifting Plants Needs to be Addressed

- Over the last year a White Paper has been drafted to modify the
current TGD and Fe / Cu limits for base loaded plant

- Plant monitoring worldwide (Denmark, UK, Australia and New

Zealand) has been conducted and subjected to a statistical
analysis, and will be continued in 2020 (older, AVT(R), & Cu units)

- The first version of an IAPWS Map for “Decay of Corrosion

Products following Startup of Fossil and Combined Cycle Plants”
has been developed.

- White Paper was presented at IAPWS Meetings in Banff, Canada,

October 2019
 New. Technical Guidance Documents
Monitoring Iron in Flexible Plants (White Paper 2018)

Initial Concept of IAPWS Map for Decay

of Corrosion Products During Startup

Improving Shutdown &

Startup Chemistry
 IAPWS Procedure to Quantify CP Transport
During Startup

Example: Startup of a Danish CCGT

• Summary of procedure
• Flush feedwater sample point as
soon as pressure is available
• Measure and register oxide levels in
feedwater by proxy methods during
startup
• Take samples for filtered iron
intermittently to establish correlation
to proxy results
• Note times for milestones: First fire,
by-pass, turbine roll-up,
synchronisation etc.
• Plot iron levels versus time after First
fire, mark milestones
• Integrate (iron level * feedwater flow)
from First fire to steady-state level
 iron transported to boiler during
startup plant

101 GT fire
102 FWT heating
103 Make-up
104 ST sync
Iron transported: 4.3 g

12-9-2019 CP Sampling and Analysis for Flexible Plants 18

 The IAPWS CP Decay Map
The basic guidance to optimise shutdown chemistry
Loop:
• Quantify CP transport to boiler during startup by means of
the IAPWS procedure
• Plot your plant in the Decay Map with respect CP level and
startup time
• Evaluate potential for improvement from the Decay Map
• Improve operation and preservation measures
Until you are in the optimum area

12-9-2019 CP Sampling and Analysis for Flexible Plants 19

 An Example from a Danish
Combined Cycle Plant

12-9-2019 CP Sampling and Analysis for Flexible Plants 20

1

International Association for the

Properties of Water and Steam

update on
Film Forming Substances (FFS)
 International Nomenclature

There was lots of confusion worldwide on amine

(FFA/FFAP) and non-amine (FFP) based substances.
IAPWS introduced the new nomenclature for the FFS

Film Forming Substances (FFS)

Film Forming Amines (FFA)
Octadecylamine – ODA
Oleyamine – OLA
FFA/FFAP FFP Oleyl Propylenediamine – OLDA
Film Forming Products (FFP)
Proprietary
 Film Forming Substances
IAPWS has organized three FFS Conferences (2017, 2018, 2019)
From these and the publication of two IAPWS TGD, the following
provides an outline of major topics researched and addressed
 Plant applications: fossil, combined cycle/HRSG, nuclear
industrial ammonia, fertilizer, closed cooling.
 Lots of examples of operation, shutdown & preservation, but
success results from following Section 8 in IAPWS TGDs
 Some results summarized later (good and bad)

 Thermal decomposition/thermolysis, stability – effect of

residence time, temperature, chemistry, etc. Mechanisms (?)
 For ODA degradation begins at ~450°C
 High thermal stability for OLDA up to 500°C and no
significant increase of formate and acetate
 Higher stability compared to alkalizing amines
 Lower degradation with increasing pH 8.5 – 9.6
SLIDE 23

Sources at IAPWS FFS Confs: Xue, De Mayer & Vidojkovic (Ghent), Roy (CEA)
 Film Forming Substances
IAPWS has organized three FFS Conferences (2017, 2018, 2019)
From these and the publication of two IAPWS TGD, the following
provides an outline of major topics researched and addressed
 Film formation
 Detection visually (multiple plants), Laboratory - XPS, EIS
 Water touched surfaces have hydrophobicity. Steam circuit
results remain variable
 ODA Films remain stable up to 30+ days of wet/dry shutdown

 Adsorption on surfaces. Laboratory work on metal surfaces.

 Higher adsorption rate and coverage with temperature, and
appears highest on copper and carbon steel

 FAC. Good experience in plants for single- and two-phase

FAC, but some questions for latter in laboratory tests.

SLIDE 24

Sources at IAPWS FFS Conferences: Roy (CEA), Hater (Kurita), Lister (UNB)
 Film Forming Substances
From the literature and previous IAPWS FFS Conferences:
The following claimed and/or observed benefits of FFS led us to look in
detail at the oxides which grow throughout generating plants

 Suitable for all-ferrous and mixed-metallurgy (copper

alloys) feedwater systems
 Lower corrosion product generation and transport
 Cleaner steam turbines
 Benefits for oxidizing and reducing chemistries
 Avoids BTF / HTF due to Under-deposit Corrosion &
Corrosion Fatigue
 Shutdown protection under wet and dry conditions
 Arrested FAC (single- and two-phase)
 Arrested ACC corrosion / FAC

Most obvious example in ACC 

SLIDE 25
 ACC Two-phase FAC can be “Arrested” with FFS
(Significant Reduction in DHACI for FAC at Tube Entries in ACC
Accompanied by Significant Reduction in Total Iron in Condensate)

DHACI 4
Cross member
appear to arrest
using FFS

DHACI 1

Courtesy Bill Stroman

SLIDE 26
 Film Forming Substances
However, from plant assessments there have also been numerous
“reported” problem areas following application of FFS which again led
us to think about oxides

 Increased oxide deposits in Boilers (tubes, drums) and

Turbines
 UDC tube failures due to heavy oxide deposits
 Increased boiler / HRSG evaporator oxide deposition
 Increased levels of deposits in tubes, headers, drums
 Variable detailed documentation of FAC (especially
before FFS)
 Variable detailed documentation of ACC corrosion/FAC
(before FFS)

One example 
SLIDE 27
 HP Evaporator Heavy Deposits and Failure
Double Pressure HRSG (9 and 0.5 MPa). HTF after FFAP Application
with no IAPWS Section 8 Review Before Application

SLIDE 28
 HP Evaporator Heavy Deposits and Failure
Double Pressure HRSG (9 and 0.5 MPa). HTF after FFAP Application
with no IAPWS Section 8 Review
Severe Under-deposit
Corrosion in typical multi-
laminated morphology

SLIDE 29
 Technical Guidance Documents
Film Forming Substances
Base Case Guidance
1. Operation. All-ferrous fossil, combined cycle and
biomass plants – “Section 8”
- Which FFA to use
- “Monitoring 1” baseline before use
- How much to dose and where
- How to analyze content of FFA in cycle
- How to determine optimum use (Monitoring 2)
Customization Guidance
2. Shutdown/Layup
3. Different FFP and Combinative Mixtures
4. Major Components with Copper or Aluminum
5. Different Temperature / Pressures
6. Systems with ACC and Condensate Polishers
7. Seawater cooling and Desalination
IAPWS TGD8-16 is only Guidance Worldwide for FFS.
Revision September 2019
 New Technical Guidance Documents

Film Forming Substances - Nuclear Plants

- International interest in developing IAPWS White

Paper from the nuclear community worldwide
(Canada, France, Germany, Japan, UK)
(White Paper, September 2020, Torino, Italy)

Film Forming Substances - Industrial Plants

- The same international team involving all the

chemical suppliers who participated in the
development of the FFP TGD for fossil and
combined cycle plants plus others involved
directly in industrial plants
(Published, October 2019, Banff, Canada)
 New Technical Guidance Document

Chemistry Management in Generator Water

Cooling during Operation and Shutdown
The generator is a single point of failure for the whole power plant,
with no redundancy

Generator with output > 400 MW usually have water cooling of the
stator

Key chemistry related problems with generator water cooling:

• Flow restrictions in the stator cooling channels by Copper oxides

• Clogging of filters and strainers by Copper oxides
• Corrosion attack of materials
 Generator Cooling Water Chemistry

Background science on the behavior of Cu in generator cooling

water systems

Requirements for generator water chemistry:

• Water chemistry parameters for normal operation
- use of high purity water
- high oxygen chemistry (> 2000 µg/kg)
- low oxygen chemistry (<20 µg/kg)
- alkalization of the water (pH 8.5 – 9.0, using NaOH)
• Layup during shutdown
• System and component design
• Special operating routines
Generator Cooling Water Chemistry:
Customization

IAPWS TGD Published in October 2019

 International Conferences
Future Meeting Bookmarks:

IAPWS Annual Meeting

6th – 11th September 2020.
Torino, Italy
- Includes Thermophysical Properties, Seawater, Ice,
Humidity, Power Plant Chemistry, Physical
Chemistry of Aqueous Solutions

European HRSG Forum – EHF2020

26th – 28th May 2020. Strasbourg, France

4th FFS International Conference

10th – 12th March 2020. Strasbourg, France
 IAPWS Technical Guidance Documents for
Fossil and Combined Cycle Plants & with ACC
• Procedures for the Measurement of Carryover of Boiler Water
and Steam (September 2008). This document includes the
procedures to measure carryover from drum boilers to assist in
preventing steam turbine failure/damage. TGD1-08

• Instrumentation for monitoring and control of cycle chemistry

for the steam-water circuits of fossil-fired and combined-cycle
power plants (September 2015). This document includes a table
that can be used to determine the minimum key level of
instrumentation required for any fossil or combined cycle/HRSG
plant. Also addresses fast and/or frequently started units. TGD2-09(2015)

• Volatile treatments for the steam-water circuits of fossil and

combined cycle / HRSG power plants (July 2015). This document
includes the basis for AVT and OT for all plants with customization
for plants with ACC and using ammonia and amines. Recently
added guidance for fast and/or frequently started units. TGD3-10(2015)

Freely available and downloadable on IAPWS website www.IAPWS.org

 IAPWS Technical Guidance Documents
Fossil and Combined Cycle Plants & with ACC
• Phosphate and NaOH treatments for the steam-water circuits of
fossil and combined cycle / HRSG power plants (Oct 2015). This
document includes the basis for selecting the optimum boiler/HRSG
evaporator water treatment for (phosphate and NaOH treatments)
for all plants with drum units. TGD4-11(2015)

• Steam Purity for Turbine Operation (Sept 2013). This document

covers guidance for a wide range of turbines (fossil, nuclear,
industrial, geothermal, etc) and failure mechanisms. It includes
customizations for plants using amines and with carbon dioxide.
TGD5-13

• Corrosion Product Sampling and Analysis (May 2014). This

document covers the optimum procedures and techniques for
monitoring iron and copper. Includes a table of achievable iron
levels for plants including those with ACC. TGD6-13(2014)

Freely available and downloadable on IAPWS website www.IAPWS.org

 IAPWS Technical Guidance Documents
Fossil and Combined Cycle Plants & with ACC
• HRSG HP Evaporator Sampling for Internal Deposit
Identification (Sept 2016). This document includes the locations
where to take samples from HGP and VGP HRSGs, how to analyze
the samples, and an IAPWS map to assist in determining whether
the HRSG HP evaporator needs to be chemically cleaned. TGD7-16

• Application of FFS in Fossil, Combined Cycle and Biomass

Plants (Revision October 2019). This document covers optimum
application guidance for FFA / FFAP / FFP in all-ferrous plants. It
also includes customizations for shutdown / layup, multiple
pressures, mixed-metallurgy feedwater systems, condensate
polishing, and units with ACC. TGD8-16(2019)

• Air In-leakage (Sept 2018). This document covers guidance for the
monitoring and control of AIL for a wide range of fossil, biomass,
nuclear, and industrial plants including those with ACC. The major
performance and cycle chemistry aspects are included. TGD9-18

Freely available and downloadable on IAPWS website www.IAPWS.org

 IAPWS Technical Guidance Documents
Fossil and Combined Cycle Plants & with ACC
• Application of FFS in Industrial Steam Generators (October
2019). This document covers optimum application guidance for FFA
/ FFAP / FFP in industrial plants. It also includes customizations for
shutdown / layup, multiple pressures, mixed-metallurgy and
aluminum feedwater systems, condensate polishing, units with ACC,
special boiler types and with poor makeup. TGD11-19

• Chemistry Management in Generator Water Cooling (October

2019). This document covers guidance for all generators with
water-cooled windings. The high - and low - oxygen chemistries for
operation and shutdown are included.
TGD10-19

Freely available and downloadable on IAPWS website www.IAPWS.org

 Resources for all areas of water and
steam

Freely available and downloadable on IAPWS website

- www.IAPWS.org

Please give full attribution to IAPWS