Engineering Failure Analysis 96 (2019) 538–542

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Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Short Communication

Temper embrittlement of 9%Ni low carbon steel

T
⁎
S.S.M. Tavaresa,b, , R.P.C. da Cunhab, C. Barbosac, J.L.M. Andiad
a
Universidade Federal Fluminense, Rua Passo da Pátria, 156, CEP 24210-240 Niterói, RJ, Brazil
b
Centro Federal de Educação Tecnológica Celso Suckow, Rio de Janeiro/Brazil
c
Instituto Nacional de Tecnologia, Centro de Nanomateriais, Rio de Janeiro/Brazil
d
Instituto SENAI de Tecnologia de Solda, Rio de Janeiro, Brazil

A R T IC LE I N F O ABS TRA CT

Keywords: This study investigates the correlation between the microstructure and fracture characteristics of
Temper embrittlement a 9% Ni low carbon steel tempered at 400 °C. This material is used in cryogenic services in oil and
Cryogenic steel gas industries. The un-correct tempering temperature selection may cause temper embrittlement
9%Ni steel (TE), which drastically decreases the cryogenic toughness of the steel. This phenomena was in-
vestigated in specimens with fine and coarse previous austenite grains. The fracture surfaces of
temper embrittled specimens were characterized by intergranular cracks and quasi-cleavage fa-
cets. Fe3C intergranular particles were found to be the main microstructural evidence and the
cause of temper embrittlement in the 9%Ni low carbon investigated, as observed by detailed
scanning electron microscopy with elemental microanalysis.

1. Introduction

9% Ni low carbon steels have been used in cryogenic services in pressure vessel plates (liquefied natural gas storage tank, for
example), pipes and accessories for low-temperature due to its high toughness at temperatures as low as −196 °C. In a comparison to
austenitic stainless steels (AISI 304, 304 L and similar) 9%Ni low carbon steels have higher mechanical resistance, which means
lighter constructions. For instance, the minimum specified yield limit of an annealed AISI 304 L is 205 MPa (30ksi) [1], while the
plate of 9%Ni low carbon steel quenched and tempered in the 565–605 °C has a minimum yield limit of 586 MPa (85 ksi) [2].
Although one of the objectives of the tempering treatment is to increase the toughness of martensitic steels, un-correct tempering
temperature selection may cause a brittle behavior in a number of families of steels. Several brittle failures of quenched and tempered
steels are attributed to temper embrittlement (TE) or tempered martensite embrittlement (TME) [3–6].
Temper embrittlement in CreMo and Ni-Cr-Mo alloy steels has been attributed to impurities segregation in previous austenite
grain boundaries, especially phosphorus [3–6]. Temper martensite embittlement of low alloy steels is frequently attributed to aus-
tenite decomposition into Fe3C in the interlath region of martensite plates when the steel is tempered at temperatures in the
260–370 °C range [6]. However, the characteristics of TME and TE may be very similar, despite of innumerous attempts to separate
them. For instance, Marterkowski and Krauss [7] investigated low and high phosphorus SAE 4340 steels and found that Fe3C pre-
cipitation and phosphorus segregation are the main causes of TME. According to Jarvis and Bulloch [8] TME leads to transgranular
failure (through prior austenite) while TE, which they called Reverse Tempering embrittlement (RTE), is impurity controlled and
occurs after tempering at higher temperatures, resulting in intergranular failure along existing prior austenite grain boundaries.
In this work, the temper embrittlement phenomena of a 9% Ni low carbon steel was studied. According to Q. Ahsan et al. [9]

⁎
Corresponding author at: Universidade Federal Fluminense, Rua Passo da Pátria, 156, CEP 24210-240 Niterói, RJ, Brazil.
E-mail address: ssmtavares@id.uff.br (S.S.M. Tavares).

https://doi.org/10.1016/j.engfailanal.2018.11.011
Received 19 October 2018; Accepted 27 November 2018
Available online 28 November 2018
1350-6307/ © 2018 Elsevier Ltd. All rights reserved.
S.S.M. Tavares et al. Engineering Failure Analysis 96 (2019) 538–542

Table 1
Chemical composition of 9%Ni-low carbon steel studied.(% wt).
C Mn Ni Si P S Ti Al

0.062 0.64 9.54 0.259 0.01 0.01 0.014 0.023

temper embrittlement of 9%Ni steels is reported to occur in the 370–540 °C range. Specification standards [2,10,11] recommend
tempering in the 565–605 °C range after quenching or double normalizing treatments. This treatment produces a microstructure of
ferrite and iron carbides (tempered martensite), with reverse austenite. This combination provides very high impact toughness
Charpy at −196 °C. However, if the steel is tempered around 400 °C, the low temperature toughness is severely decreased. The goal of
this work was to investigate the cause of temper embrittlement of the 9%Ni low carbon steel tempered at 400 °C. The effect of
previous austenite grain size on the embrittlement effect was also investigated.

2. Experimental

2.1. Material

The material studied in this work was from of seamless pipe of a 9% Ni low carbon steel (composition shown in Table 1). It was
cut and machined to dimensions close to the sub-size Charpy specimen (11 × 8 × 5 mm3). Specimens were water quenched from two
different soaking temperatures (820 °C and 1000 °C). Then the specimens were tempered at 400 °C and 600 °C for 1 h, and finally
machined to the dimension of sub-size Charpy specimens (10 × 7.5 × 55 mm3) with V-notch.
Two austenitizing temperatures were used in order to obtain different previous austenite grain sizes. Table 2 describes the heat
treatments and specimens identification.

2.2. Microstructural investigation

All specimens were prepared for microstructural investigation in optical microscope and scanning electron microscope (SEM)
with energy dispersive spectrometer (EDS) and wavelength dispersive spectrometer (WDS) for elemental microanalysis.
Specimens were prepared by grinding, mechanical polishing and etching. For general microstructure the specimens were etched
with Nital 2%. For previous austenite grain size (PAGS) determination a special reagent composed of 15 g picric acid, 5 ml of
potassium chromate, 625 ml of distilled water and 275 ml of neutral detergent was used.

2.3. Mechanical tests (impact Charpy and hardness)

The impact tests were carried out at −196 °C with sub-size V-notched Charpy (7.5 mm) specimens in a Universal Pendul with
maximum energy 300 J. After tests, the fracture surfaces and microstructures were examined in the scanning electron microscope.
Vickers hardness tests were performed with 10 kgf load.

3. Results and discussion

Fig. 1(a) and (b) show the impact toughness and hardness variation with heat treatments. Due to the larger grain size, specimens
quenched from 1000 °C have lower toughness than those austenitized at 820 °C. This was evident in the as quenched specimens and in
the quenched and tempered ones. Fig. 2(a-b) compares the microstructures of as quenched specimens. The etching used revealed the
previous austenite grain boundaries, making easy the quantification. Specimens austenitized at 820 °C have an average grain size
15.9 μm (ASTM 8.75) while specimens austenitized at 1000 °C have an average grain size 89.9 μm (ASTM 4.17).
Tempering at 400 °C caused severe embrittlement in the 9%Ni steels, as expected from previous works [9,12]. In 9%Ni low carbon
steels embrittlement occurs without hardening, as shown in Fig. 1(b). Fig. 3(a-b) show the fractography of specimens Q1-T400 and
Q2-T400. Both are brittle fractures with intergranular cracks and quasi-cleavage facets. According to Dieter [13], quasi-cleavage is
related but distinct to cleavage fracture. It is often observed in low temperature fracture of quenched and tempered steels. The quasi-
cleavage facets are not true cleavage planes, but correspond in size to prior austenite grains. In specimen Q2-T400 the previous
austenite grains are coarser, and some regions with very small microdimples are also present, which is also a characteristic of quasi-

Table 2
Heat treatments and specimens identification.
Austenitizing temperature (°C) Tempering

400 °C/1 h 600 °C/1 h

820 °C (Q1) Q1-T400 Q1-T600

1000 °C (Q2) Q2-T400 Q2-T600

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S.S.M. Tavares et al. Engineering Failure Analysis 96 (2019) 538–542

Fig. 1. (a) Toughness and (b) hardness variation with heat treatments.

Fig. 2. Microstructure with previous austenite grain boundaries revealed for quantification: (a) Q1; (b) Q2.

Fig. 3. Fracture surfaces of specimens from (a) Q1-T400 and (b) Q2-T400.

cleavage fracture [13].

Fig. 4 shows the microstructural characterization by SEM of specimens Q1–400 and Q2–400 etched with nital 2%. Q1–400 has
fine light micro-constituents along prior austenite grains, while coarser particles are observed in Q2–400. The correlation with the
toughness results suggest that these could be M-A constituents or Fe3C carbides precipitated in the prior austenite grain boundaries
and between martensite laths. Figs. 5 and 6 show intergranular particles with high magnification. In Fig. 5 an EDS map of carbon
content is shown in detail. Since EDS is rather qualitative for light elements, WDS was performed in points 1 (matrix) and 2 (in-
tergranular particle) of Fig. 6. The results shown in Table 3 are semi-quantitative, considering that the particle is too small to be

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S.S.M. Tavares et al. Engineering Failure Analysis 96 (2019) 538–542

Fig. 4. Microstructure of specimen water quenched from 820 °C and tempered at (a) 400 °C and (b) 600 °C.

Fig. 5. Intergranular particles and EDS carbon map in detail.

Fig. 6. Microstructure with points of matrix and intergranular particle analyzed by WDS (see results in Table 2).

analyzed isolated. Despite of this, the high carbon content (4.03%) and the low nickel content (8.46%) obtained in point 2 suggest
that the intergranular particle is an iron carbide type Fe3C. These intergranular particles are the cause of intergranular embrittlement
observed.

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S.S.M. Tavares et al. Engineering Failure Analysis 96 (2019) 538–542

Table 3
WDS results of points 1 and 2 from Fig. 6.
Element Point 1 (matrix) Point 2 (particle)

C 0.197 4.03
Al 0.021 0.019
Si 0.236 0.256
S 0.001 0.002
Ni 8.581 8.460
Fe Bal. Bal.

4. Conclusions

9%Ni low carbon steels show temper embrittlement when tempered at 400 °C. The fracture surface contains intergranular cracks
and quasi-cleavage facets.
Fe3C intergranular carbides were identified by SEM with EDS and WDS. These particles are the microstructural feature which
provokes intergranular embrittlement.

Acknowledgement

This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance
Code 001. Authors are also greatful to Brazilian research agencies CNPq and FAPERJ for financial support.

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