FAILURE ANALYSIS OF HEAT RESISTANT ALLOY IN

PROCESS GAS ENVIRONMENT

Sundeep Parikh, Material Technology Development Centre, Bombay.

ABSTRACT :

A failure in the HP-40 Mod. Nb heat resistant alloy reducer resulted in fire on 8th

June’2000. The reducer which had a design life of 1,00,000 hours (11 years) failed suddenly

after 4 years of service. M/s. Material Technology Development Centre were retained for

carrying out failure analysis studies. Investigations show that the reducer is functioning

in temperature range of 900°C at 4.5 kg/cm² pressure wherein it is exposed to process

gas ( 75% H2 and 15% CO ) environment. At temperatures of operation alloy degradation in

carbonaceous gases results in internal carburization and metal dusting has occurred. The

mechanism operative is determined to be the one documented by H.J. Grabke etal. Metal

dusting of internal diffuser of nickel material leading to carbon build up within restricted

geometry results in cementite ( Fe3C) precipitation in HP 40 mod Nb. Presence of H2S

leads to stabilizing of Fe3C ( Cementite) in HP40 mod. Nb. This embrittles the alloy and

the original creep behavior and life of the alloy as per the Larssen Miller Parameter is not

possible resulting in failure.

INTRODUCTION :

A heat resistant alloy failed in service after 4 years of operation. The failure was detected in

service by an operater when a through thickness flame was detected. Photograph 1

shows the typical reducer assembly. Tables 1,2 & 3 show the chemical composition,

mechanical properties, and life at elevated service temperatures for this alloy as per design

data/specifications sheets. As a class of materials this alloy can be classified as heat

resistant alloy (Fe-Cr-Ni) and preferred material for elevated temperature service wherein a

combination of properties of

1. Resistance to creep and Stress Rupture

2. Resistance to corrosion, oxidation and carburization at elevated temperatures

3. Sufficient ductility to failure

4. Stable structure and properties over a given time

5. Mechanical workability (weldability, machinability etc)

are required. However, the selection of a specific alloy depends on the prevalent set of

requirements as per the operating conditions. In the current case, the reducer was

operating in the temperature range of 850°C to 900°C and operating at a pressure of 4.5

kg/cm″. At these operating parameters, the reducer has a design life of 11 years and thus

the failure after 4 years as evidenced herein is deemed as premature failure. Thus failure

analysis investigations were undertaken to determine the cause of premature failure and

to determine the remedial measures that would prevent the recurrence of similar failure

and thus plant shutdown. At this stage we present some theoritical aspects of metal

dusting and the mechanism as documented by Grabke≥, as the same is relevant to this

case study.

Theory of Metal Dusting and Grabke’s Mechanism :

As per the ASM handbook, metal dusting is an accelerated

deterioration of metals in carbonaceous gases at elevated temperatures to form

a dust like product and is frequently encountered mode of corrosion that is associated

with carburizing furnaces. It tends to occur in regions where carbanaceous gases

become stagnant and the alloy suffers rapid wastage resulting in corrosion

products consisting of carbon soots, metal, metal carbides and oxides. The attack
generally initiates from metal surface that is in contact with furnace refractory.

The phenomena of metal dusting has been seen in chromium steels, austenitic

stainless steels, and nickel and cobalt base alloys. Its occurance has been reported

as oxidation of carburized metal in petrochemical plants. The temperature range

for metal dusting phenomena is 480°C – 815°C, however, it has also occurred

in range of 1095° C in strongly reducing atmospheres containing H2 . Thus it is

necessary to understand the mechanism , the operative ranges of parameters

which facilitate metal dusting and the methods of prevention of same. Accordingly

these are considered herein in the light of the research & development work of late

‘90s as explained by Grabke etal≥. However, prior to that carburization and metal

dusting as understood currently by various reasearchers are explained as

under.

Carburization :

Carburization is an internal carbide formation at high temperatures and carbon activities

ac < 1 leading to embrittlement, cracking and loss of oxidation resistance.

Metal Dusting :

Metal dusting is disintegration of metals to a dust of carbon and metal particles in

carbonaceous gas environment at ac >1 and it can occur at any temperature.

In the late 90’s, extensive research work carried out at Max Planck Institute ≥

has resulted in a better understanding of the thermodynamics, mechanisms and

Kinetics of metal dusting phenomena. Accordingly, the mechanism, as proposed

by Grabke etal≥, best describes the sequential events in metal dusting

phenomena. As per this the mechanism metal dusting in Fe / steel

materials is as under,
For Iron and Fe base alloys the reaction sequence is;

1. Transfer of C into the metal phase and over saturation of the metal, ac > 1

2. Formation of cementile M3 C ( M=Fe,Ni) at the surface which acts as a

barrier for further C- ingress thus causing.

3. Graphite precipitation decreasing the carbon activity on cementile to ac =1,

whereby M3 C becomes unstable and decomposes according to

M3 C C + 3M.

4. The carbon atoms from this decomposition are attached to basal planes of

graphite which grow into the cementile. The atoms diffuse through the

graphite and agglomerates to small particles ( about 20 nm diameter).

5. These particles act as catalyst for further C- deposition and vast coke growth

results.

Their studies have also shown that presence of sulfur inhibits the mechanism.

Adsorbed sulfur effectively hinders step ( 3) , the nucleation of graphite

and in this way interferes with the mechanism. The adsorbed sulfur

stabilizes the cementite and one can grow thick layers of cementite on

iron and steel.

PRELIMINARY EXAMINATION AND VISUAL OBSERVATION

Preliminary examination revealed a flat fracture indicative of lack of ductility at the time of

failure. Apparently the failure, which was at knuckle portion, was inside to outside. The

brittle nature of fracture is shown in photographs in annexure. Photographs 1,2, and 3

show the crack location, fitup and external view of a process gas reducer. Fig. 1

shows the schematic of the reducer assembly indicating the crack location. Functionally the

reducer is working in a process gas environment comprising of a gas chemistry of

75 % H2 , 15 % CO and 10 % CH4 by volume. This process

gas is transferred through the internal guide tube of inconel to the reactor for reducing

the materials within the same. For prevention of heat loss the process gas which

is at a temperature of 900°C and pressure of 4.5 kg/cm″ the reducer was externally

insulated using insulation wool. Holes were seen inside the guide tube. Some pitting

on the inside of reducer was also seen. The crack can be described as a

hairline circumferential crack.

TESTING & RESULTS :

Physical, chemical and metallography analysis were conducted as per ASTM standards

recommended. The results of the physical and chemical analysis are tabulated in Tables 4 &

1 The deviation in the tensile values has been attributed to the short tensile coupon piece

that was generated due to the limitation of configuration and sample size. Metallography

indicated an as cast dendritic structure with evident carbides in an austenitic matrix for a

new reducer and an as cast dendritic structure with grain boundary carbides in the failed

component. This grain boundary carbides was not restricted to the area of crack but was also

found in the area away from the knuckle portion that had cracked. Short term elevated

temperature tests to determine the effect of temperature on microstruct ure were carried out

at 950°C. These short term tests did not reveal grain boundary carbide precipitation after

750 hours at 950°C in absence of any media. The results of these study are tabulated in

Table 5. As documented, a change in morphology of the precipitates seems to have taken

place but the grain boundary precipitation could not be confirmed. Chemical analysis and

metallography of the internal nickel guide tube were carried out. Metallography indicated

pitting and grain boundary precipitation in the same.

DISCUSSIONS :

On the basis of the visual observation, discussions with the plant personnel, and the results of

the testing, the failure as per the schematic in Fig. 2 was reconstructed. As evident from

this the failure occurred in the kuncle region of the reducer adjacent to the weld heat affected

zone. The fracture surface was flat. The failure apparently seems to be from inside to outside

and the inside surface exhibited pitting at the area of crack. The results of the chemical

analysis of the nickel tube, the reducer itself and the gas chemistry did not reveal any

deviation from the designed specified limits as is seen from Table 6 and Table 7.

Metallography revealed precipitation of the carbides along the grain boundaries at and away

from the region of the crack. Visually holes were evident indicative of deterioration /

degradation over the period of service life in the nickel guide tube. The formation of these

holes have been attributed to the phenomena of metal dusting in nickel tubes. As per Grabke

et al in case of nickel base alloys metal dusting process involves direct graphitization and

metal disintegration involving no intermediate M3 C precipitation. Thus the inside tube

disintegrates and the metal dusting of the nickel base alloy results in the carbonaceous gases

coming into contact with the heat resistant alloy and leads to an increase in carbon activity at

the knuckle region. The diffusion of carbon into the alloy matrix & the precipitation of M3 C

at the grain boundaries now is energetically facilitated. Thus the results of the

metallography which exhibit carbide precipitation at grain boundary are explained in light of

Grabke’s mechanism. As per Monkman & Grant any precipitation at grain boundary affects

the ductility at rupture for the empirical relationship for creep rupture life proposed by them.

Ramanarayan et al have also concluded in their work that the mechanical stability of the heat

resistant alloys is affected when tested in presence of carbon environment corrosion.

Thus we explain the results of the observations, tests and investigations in light of work of

above scientists as a results of carburization and metal dusting and the sequential set of the

events leading to the premature failure of the process gas reducer as under,

1. Carburization and metal dusting of the inside nickel guide tube

2. Carbon diffusion into the matrix and formation of M3 C (cementite or Hagg’s

precipitate)

3. The grain boundaries act as favourable site for nucleation of these precipitates.

4. Increase in the internal stresses and a volume shrinkage because of this precipitate.

The role of residucal stresses is HAZ has been considered as minimal. However, the

same may have been superimposed on operating stresses but could not be confirmed

in our studies.

5. Degradation in creep life resulting in premature failure after 4 years rather than the

designed life of 11 years as per Larsen Miller parameter curve for the alloy.

CONCLUSION :

Failure occurred because of metal dusting in presence of the carbonaceous gases as a result

of increse in carbon activities in the knuckle portion of reducer. Th operative mechanism has

been the one proposed & documented by Grabke for iron base alloys. This embrittles the

alloy due to corrosion in presence of carbon environment & leads to altering of creep

behavior and design rupture life of alloy is not possible.

REFERENCES :

1. ‘Metal Dusting’ ASM Handbook Volume 13, ninth edition, pp.9, 1312-1313,

2. “ An empirical relationship between rupture life & minimum creep rate”, F.C.Monkman

and N.J.Grant, Proceedings ASTM Vol .56, 1956, P.593

3. Corrosion by carbonaceous gases, carburization & Metal dusting, methods of prevention’,

H. J. Grabke Max-planck institute, Germany, 1998.

4. Kinetic studies of coke formation & removal on HP-40 in cycled atmospheres; steurbant,

Grabke, Stobbe, Vanburm, Korf, Defranca, Materials & Corrosion 49,1998

5. Carbon – induced Corrosion of Metals & Alloys, T.A Ramanarayanan, C.M. Chum, & J.D

Mumford, Material Science Forum Vols. 369-372 (2001), PP 55-76

Table 1 : Chemical Composition of heat resistant alloy

Elements As specified Failed Reducer Test Piece

%C 0.35 - 0.45 0.41 0.53

%S - 0.02 0.11

%P - 0.023 0.023

% Mn 1.5 max 1.020 0.59

% Si 1.5 Max 1.62 1.82

% Cr 23.00 – 27.00 24.69 25.4

% Ni 33.0 – 37.0 35.70 41.96

% Mo 0.5 max 0.12 0.10

% Nb 1.0 – 1.5 1.09 1.02

% Fe Balance Balance Balance

Table 2 : Mechanical Properties of alloy as per data sheets at elevated

temperature

Sr.no Temperature °f T.S. Psi Y.S Psi % El

1 1600 °f 24,800/- 18,300/- 25

2 1700 °f 18,600/- 14,400/- 30

3 1800 °f 14,600/- 11,600/- 35

4 1900 °f 11,200/- 10,000/- 45

5 2000 °f 9,000/- 8,200/- 47

Table 3 : Average stress for 1,00,000 hour rupture life as specified in data
sheet as a function of temperature.

Sr.no Temperature Stress as specified

(Psi)

1. 1600ºf 4720

2. 1700ºf 3050

3. 1800ºf 1840

4. 1900ºf 1040

5. 2000ºf 550

Table 4 : Yield & Ultimate stress of heat resistant alloy at elvated

temperature

Sr.no. Temperature in ° C YS UTS

MPa Mpa
1. 250º C 249 416

2. 700º C 185 336

3. 800º C 177 328

Table 5 : Results of Metallography after short term elevated exposure tests

Sr.no. Exposure time Micro Structure observed

1. Nil As cast austenitic structure with

dendritic carbides

2. 162 hours As cast dendritic structure

No grain boundary precipitation

3. 282 hours As cast dendritic structure

4. 720 hours As cast denrdritic structure in

austenitic matrix

5. 4 yrs * Grain boundary carbides

Table 6 : Chemical analysis of the nickel tube

Elements Test Piece. Alloy 800 HT

Ni 36.5 30-35

Cr 16.68 19-23.00

Fe Bal. 39.5 min

Ti 0.076 0.15-0.60

Al - 0.15-0.60

C 0.01 0.06-0.1

Mn 0.33 1.5

Si 0.20 1..0

Other - 0.85-1.20 Al
+ Ti
 Table 7 : Chemistry of Process Gas as specified by volume Percent

Chemical
volume H2 CO CO2 N2 CH4 H2O C2H6
Percent

Design 68.6 16.03 3.04 1.71 9.26 1.34 0.02

Operation 70.33 15.15 1.49 1.90 9.84 1.27 0.02