Technical Module Work Group March 2000

BRD Appendix V HTHA Module

Table of Contents

TECHNICAL MODULE #3 HIGH TEMPERATURE HYDROGEN ATTACK (HTHA)...

Scope...................................................................................................................................................1
Technical Module Screening Questions................................................................................................2
Basic Data............................................................................................................................................2
Background Information.......................................................................................................................3
Determination of Susceptibility............................................................................................................5
Inspection Effectiveness........................................................................................................................6
Determination of Technical Module Subfactor......................................................................................9

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Technical Module Work Group February 1999
BRD Appendix V Page 1 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Scope
High temperature hydrogen attack (HTHA) occurs in carbon and low alloy steels exposed to a
combination of high hydrogen partial pressures and elevated temperatures. HTHA occurs when
atomic hydrogen diffuses into the steel and reacts with carbides in the microstructure. There are
two reactions associated with HTHA. First the hydrogen molecule, H2, must dissociate to form
atomic hydrogen, H, which can diffuse through steel.

H2 2H (dissociation of hydrogen)

Because atomic hydrogen forms more readily at high temperatures and high hydrogen partial
pressures, the potential for HTHA increases as the temperature and hydrogen partial pressure
increase. The second reaction, between the atomic hydrogen and metal carbides, occurs inside the
microstructure to form methane.

4H + MC CH4 + M

HTHA damage manifests itself in two forms:

1. Internal decarburization and fissuring caused by the accumulation of methane at the carbide-
matrix interface.
2. Surface decarburization resulting from the reaction of the atomic hydrogen with carbides at or
near the surface where the gas can escape without causing fissures.
Internal fissuring is more typical in carbon and C-1/2Mo steels, and at high hydrogen partial
pressures, in Cr-Mo steels. Surface decarburization is more common in Cr-Mo steels at high
temperatures and low hydrogen partial pressures.

Increasing the alloy content of the steel to increase carbide stability reduces the potential for
HTHA damage. Carbon steel, which contains iron carbide (Fe3C), is significantly less resistant to
HTHA than Cr-Mo steels that contain stable and HTHA resistant Cr and Mo carbides.

Historically, industry experience has been used to predict HTHA resistance. This experience has
been used to create temperature-hydrogen partial pressure curves for a number of carbon and low
alloy steels. Each curve shows combinations of temperature and hydrogen partial pressure where
a given grade or type of steel has been successfully used without HTHA damage. These curves,
usually referred to as the Nelson curves, are maintained in API Recommended Practice 941 based
on industry experience.

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Technical Module Work Group February 1999
BRD Appendix V Page 2 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Technical Module Screening Questions
The screening questions for HTHA listed in Table TM3.1 are used to determine if the module for
HTHA should be entered.

Table TM3.1 Screening Questions for HTHA Module

Screening Questions Action

1. Is the material carbon or low alloy steel? If Yes to both, proceed to

2. Is the operating temperature >400F and operating hydrogen partial module for HTHA.
pressure >80 psia?

Basic Data
The data listed in Table TM3.2, if available, can be used to estimate susceptibility of HTHA for
carbon and low alloy steels. If exact process conditions are not known, consult a knowledgeable
process engineer to obtain the best estimates.

Table TM3.2 Basic Data Required for Analysis

Basic Data Comments

Material of Construction Determine the material of construction of the equipment/piping 1.

Determine the hydrogen partial pressure, which is the product of

Hydrogen Partial Pressure (psia) the mole fraction of hydrogen and the total absolute pressure.

Temperature (degrees Farenheit,F) Determine the temperature of exposure. This is the maximum
operating temperature, TOP.

Determine time of exposure in hours. This is the time in service,

Time (hours)
tSERVICE.
1
Recent experience has shown that original heat treatment condition is not a good way to reflect carbide
stability, therefore is not considered in this model.

Det Norske Veritas (U.S.A.), Inc. Houston, Texas

Technical Module Work Group February 1999
BRD Appendix V Page 3 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Background Information
The assessment of susceptibility to HTHA could be based on the components exposure time to
high-pressure hydrogen and elevated temperatures. A single parameter, P V, has been developed to
relate time at temperature and hydrogen partial pressure. This parameter is defined in the
literature as:

PV = log(PH2) + 3.09 10-4(T)(log(t) + 14) (Eq. TM 3.1)

Where:
PH2 is the hydrogen partial pressure in kgf/cm2 (1kgf/cm2 = 14.2 psia),
T is the absolute temperature in K (K = C + 273),
t is time in hours
The Pv parameter combines hydrogen partial pressure, temperature and time based on functional
forms commonly used to parameterize the effect of service time and exposure severity on
chemical reaction rates.
As a predictor of HTHA damage, however, the
1.25 Cr-0.5Mo
Pv parameter has not produced results that have
been consistent with the industry experience. 1200
Nelson Curves
1100
Figure TM3.1 shows the Nelson curve limits PV Model Limit
Temperature (F)

1000
for 1.25Cr-0.5Mo and the PV limits for high 900
susceptibility. Below a hydrogen partial 800
pressure of 1200 psia the PV model is very 700
conservative giving high susceptibility even at 600

150 F below the Nelson curve. On the other 500

0 1000 2000 3000 4000
hand, at partial pressures higher than 1250 psia, H Partial Pressure (psia)
2
the PV model predicts that vessels operating
above the empirical Nelson curve should not Figure TM3.1. HTHA Limits for 1.25Cr-0.5Mo.
experience HTHA. While the Pv parameter has
a convenient functional form that would be suggested by fundamental reaction dynamics, these
curves show that the susceptibility of steel to HTHA is more complex than could be captured in a
single continuous function of hydrogen partial pressure and temperature.
It is for this reason that this technical module for HTHA susceptibility is based on the existing API
941 Nelson Curves. To relate susceptibility with time in service, the data from Figure 3 in API
941 was used. This data suggests that incipient attack in carbon steel is a function of the
temperature, H2 partial pressure and time. Figure 3 in API 941 shows a series of nested time
dependent, hydrogen partial pressure - temperature, curves. The curves show the combined effect
of temperature, hydrogen-partial pressure and time. Each curve represents, for a given exposure
time, the limiting pressure-temperature combinations for observed HTHA. Components exposed
to pressures and temperatures that lie above the curve for time t are likely to suffer damage before
time t. The lowest curve represents the recommended exposure limits, operating conditions
below the curve are expected to never suffer HTHA.
Figure TM3.2 shows two plots, based on these curves:

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Technical Module Work Group February 1999
BRD Appendix V Page 4 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Pressure shift as a function of time in service (PTIME). A plot of the log of the pressure
difference between the recommended limit from API941 and the curve representing time
dependent incipient attack as a function of log time.
Temperature shift as a function of time in service (TTIME). A plot of the log of the
temperature difference between recommended curve and the curve representing time
dependent incipient attack as a function of log time.
1
The slopes of these lines indicate that the temperature and pressure limits are proportional to .
t
This correlation was developed for carbon steels. It is believed that the temperature and pressure
shifts in Figure TM3.2 are conservative enough to be used for all alloys within the scope of this
technical module. This correlation is used to calculate where the Nelson Curve limits would be as
a function of time in service.

1000
Delta P
Delta T
100
Difference

10

1
10 100 1000 10000 100000 1000000
Time in Service

Figure TM3.2. Incipient attack conditions as a function of time in service.

For the purposes of this technical module, the following relationships are used to determine the
time dependent pressure-temperature exposure limits. These limits are based on recommended
limits in API 941. These limits presented as curves, Figure 1 in API 941, are denoted in this
module as:
TL(, PH2) = Temperature limit for a given pressure (from Nelson Curve), where P H2 is the
service hydrogen partial pressure.
Where the temperature shift, TTIME and pressure shift, PTIME , due to time in service, are:
1747
TTIME 5.5 (Eq.
t
TM3.2)

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Technical Module Work Group February 1999
BRD Appendix V Page 5 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

6247
PTIME 19.8 (Eq. TM3.3)
t
Where t = time in service (hours) and the constants were calculated by curve fitting the data in
Figure TM3.2.
In addition to these shifts due to time in service, this model considers what is called susceptibility
shifts (Psusc. and Tsusc). These values are defined in tables TM3.3 and TM3.4.
Once all these temperature and pressure shifts are defined, the time dependent temperature limit
for each susceptibility, TLt is calculated,
TLt(t, PH2)= TL(,NewPH2) + TTIME-Tsusc.
Where NewPH2= PH2-PTIME+Psusc

Determination of Susceptibility
Figures TM3.3 to TM3.6 show the steps to calculate the HTHA susceptibility based on the model
described above. For each set of operating conditions, the temperature limits are defined as:

TLLOW = Low Susceptibility

TLMED = Medium Susceptibility
TLHIGH = High Susceptibility

The operating temperature is then compared to these limits to define the susceptibility as indicated
in tables TM3.3 and TM3.4. The susceptibility calculation uses the existing limits from Figure 1
in API941. Carbon-1/2 Mo is not included in this figure anymore. Due to the significant number
of HTHA cases reported below the C-1/2Mo curve from Figure A-1 in API-941, for this alloy, the
limits were set from the carbon steel curve. For this reason, the susceptibility limits for C-1/2 Mo
are defined separately in Table TM3.4.

Det Norske Veritas (U.S.A.), Inc. Houston, Texas

Technical Module Work Group February 1999
BRD Appendix V Page 6 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Table TM3.3 Carbon and Low Alloy Steel Susceptibility to HTHA (except C- Mo)

Temperature Limits

High Susceptibility Medium Low Susceptibility Not

Susceptibility Susceptible
Operating Temp. TLHIGH > Operating TLMED > Operating TLLOW > Operating
>TLHIGH (Tsusc=25F, Temp. >TLMED Temp. > TLLOW Temp.
Psusc=5 psia) (Tsusc=50F, (Tsusc=75F,
Psusc=10 psia) Psusc=15 psia)

Table TM3.4 Carbon-Mo Steel Susceptibility to HTHA

Temperature and Pressure Limits

Not Low Susceptibility Medium

High Susceptibility
Susceptibility
Susceptible
Operating Temp. < TLLOW < Operating TLMED < Operating TLHIGH < Operating
TLLOW Temp. < TLMED Temp. < TLHIGH Temp.
(Tsusc=25F, (Tsusc=50F, (Tsusc=100F,
Psusc=5 psia) Psusc=10 psia) Psusc=15 psia)

Inspection Effectiveness
The nature of HTHA makes detection by conventional inspection techniques very difficult. The
following Table TM3.5 shows examples of inspection effectiveness for commonly used inspection
techniques to detect HTHA.

Det Norske Veritas (U.S.A.), Inc. Houston, Texas

Technical Module Work Group February 1999
BRD Appendix V Page 7 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Table TM3.5 Inspection Effectiveness Guidelines for HTHA

Inspection Typical Inspection Practices

Effectiveness
Category
A No inspection techniques yet available meet
the requirements of a highly effective
(Highly Effective)
inspection.
B For the suspected(1) area:
(Usually Effective) 95-100% Advanced Ultrasonic
Backscatter Technique (AUBT)
AND
follow-up with in-situ metallography or
boat samples.
C For selected(2) areas:
(Fairly Effective) 100% Advanced Ultrasonic Backscatter
Technique (AUBT),
AND
follow-up with in-situ metallography or
boat sample.
D For selected(2) areas:
(Poorly Effective) Ultrasonic backscatter plus attenuation
OR
AE of 100% total suspected area
OR
in-situ metallography or boat samples of
selected areas
E No inspection or ineffective inspection
technique used
(Ineffective)

1. Suspected areas are areas of the equipment known to operate near the Nelson Curve.
2. Selected areas are areas randomly selected by individuals experienced in HTHA, when there
are no suspected areas. These areas might include base metal, weld and heat-affected zones.

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Technical Module Work Group February 1999
BRD Appendix V Page 8 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Determination of Technical Module Subfactor
This technical module assumes that susceptibility to HTHA is determined following the steps of
the procedure outlined in figures TM3.3 through TM3.6. The susceptibility is designated as high,
medium, low or not susceptible. Based on this susceptibility rating of high, medium or low, a
severity index is assigned which reflects no inspection or monitoring credits.

As with stress corrosion cracking damage, whenever damage is found during inspection, a
significant upward adjustment is made to the subfactor. Table TM3.6 shows the interaction
between HTHA susceptibility and inspection effectiveness. Before any inspections are made the
subfactors tabulated in the first column are used. If damage is detected, the calculated
susceptibilities are irrelevant and a subfactor of 2000 is assigned to the component. In this case,
a fitness for service assessment is recommended before the component is kept in service for any
extended period of time. When an inspection finds no damage, the subfactor is determined from
the lower four rows of Table TM3.6 based on the combination of inspection results and HTHA
susceptibility. For example, three fairly effective inspections have detected no damage in a
component, which has a medium HTHA susceptibility. From Table TM3.6 the subfactor is
determined to be 80.

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Technical Module Work Group February 1999
BRD Appendix V Page 9 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Table TM3.6 Technical Subfactors Adjusted for Effective Inspection

First Inspection Two or more Inspections
Inspection Effectiveness Inspection Effectiveness

Severity Index No Poorly Fairly Usually Poorly Fairly Usually

Inspection (D) (C) (B) (D) (C ) (B)
(E)
Damage Observed - 2,000 2,000 2,000 2,000 2,000 2,000

High Susceptibility 2000 1800 1200 800 1600 800 400

Medium Susceptibility 200 180 120 80 160 80 40

Low Susceptibility 20 18 12 8 16 8 4

No Susceptibility 1 1 1 1 1 1 1

1. This table provides the technical module subfactor for various levels of susceptibility to HTHA
and level of inspection. The table also provides a technical subfactor for situations when
inspection uncovers HTHA damage. The technical module subfactor has been provided for
two inspections. Since HTHA is a time dependent damage mechanism multiple inspections
has little impact in the actual likelihood of failure. Therefore, for a greater number of
inspections, the technical module subfactors remain constant.

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Technical Module Work Group February 1999
BRD Appendix V Page 10 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Input: Top, PH2,

tservice, Material

Calculate TTIME and PTIME

using equations TM3.2 and
TM3.3

Material = YES A, to
C-1/2Mo? Fig. TM
3.5

NO

Set Susceptibility = HIGH

(1) Using Table TM3.3 (2) Calculate Total (3) NewPH2

determine Pressure Shift (Ptotal) =PH2-Ptotal
susceptibility shifts Ptotal = PTIME - Psusc
(Psusc and Tsusc)

(4) Using NewPH2 in the

corresponding curve on
Figure 1 (API941)
determine TL(,NewPH2)

B, to Calculate Adjusted Nelson Curve Limit

NO
Fig. TM (TLhigh)
Top>NCLhigh?
3.4 TLhigh= TL(,NewPH2)+Ttime-Tsusc

YES

Severity Index = High Susceptibility Number of inspections and

(Calculate TMSF using Table TM3.6) inspection effectiveness

Figure TM3.3 Determination of HTHA Technical Module Sub-factor

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Technical Module Work Group February 1999
BRD Appendix V Page 11 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Number of inspections and B, from

inspection effectiveness Fig.
TM 3.3

Severity Index = Medium Susceptibility Set Susceptibility = MEDIUM

(Calculate TMSF using Table TM3.6)

YES Following steps (1 through 4) used

for high susceptibility calculate
Adjusted Nelson Curve Limit (TLMED)
Top>TLMED?
TLMED= TL(,NewPH2)+TTIME-Tsusc

NO

Set Susceptibility = LOW

Following steps (1 through 4) used

for high susceptibility calculate
Adjusted Nelson Curve Limit (TLLOW)
TLLOW= TL(,NewPH2)+TTIME -Tsusc

Number of inspections and

inspection effectiveness

YES Severity Index = LOW Susceptibility

Top>TLLow? (Calculate TMSF using Table TM3.6)

Severity Index = NO Susceptibility

(TMSF = 1)

Figure TM3.4 Determination of HTHA Technical Module Sub-factor (Cont.)

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TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

A, from
Fig.
TM 3.3

Set Susceptibility = LOW

(5) Using Table TM3.4 (6) Calculate Total (7) NewPH2

determine Pressure Shift (Ptotal) =PH2-Ptotal
susceptibility shifts Ptotal=PTIME+Psusc
(Psusc and Tsusc)

(8) Using NewPH2 in

Carbon Steel Curve
of Figure 1 (in
(API941) determine
TL(,NewPH2)

C, to NO
Fig. Calculate Adjusted Nelson Curve Limit
TM 3.6 Top<TLLOW? (TLHIGH)
TLHIGH= TL(,NewPH2)+TTIME +Tsusc

YES

Severity Index = NO Susceptibility

(TMSF = 1)

Figure TM3.5 Determination of HTHA Technical Module Sub-factor. (Cont.). C-0.5 Mo Case.

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Technical Module Work Group February 1999
BRD Appendix V Page 13 Revision 08
TECHNICAL MODULE #3

High Temperature Hydrogen Attack (HTHA)

Number of inspections and C, from

inspection effectiveness Fig. TM
3.5

Severity Index = Low Susceptibility Set Susceptibility = MEDIUM

(Calculate TMSF using Table TM3.6)

YES Following steps (5 through 8) used for

Low susceptibility calculate Adjusted
Nelson Curve Limit
Top<TLMED?
TLMED= TL(,NewPH2)+TTIME +Tsusc

NO

Set Susceptibility = HIGH

Following steps (5 through 8) used for

Low susceptibility calculate Adjusted
Nelson Curve
TLHIGH= TL(,NewPH2)+TTIME +Tsusc

Number of inspections and

inspection effectiveness

YES Severity Index = MEDIUM Susceptibility

Top<TLHigh? (Calculate TMSF using Table TM3.6)

NO

Severity Index = HIGH Susceptibility Number of inspections and

(Calculate TMSF using Table TM3.6) inspection effectiveness

Figure TM3.6 Determination of HTHA Technical Module Sub-factor. (Cont.). C-0.5 Mo Case.

Det Norske Veritas (U.S.A.), Inc. Houston, Texas