Materials Science & Engineering A 759 (2019) 65–69

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Materials Science & Engineering A

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Short communication

Enhancement of an additive-manufactured austenitic stainless steel by post- T

manufacture heat-treatment☆
Nan Chena, Guoqiang Maa, Wanquan Zhua, Andrew Godfreyb, Zhijian Shenc, Guilin Wua,∗,
Xiaoxu Huanga,d
a
International Joint Laboratory for Light Alloys (MOE), College of Materials Science and Engineering, Chongqing University, Chongqing, 400044, China
b
Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China
c
Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, 10691, Stockholm, Sweden
d
Department of Mechanical Engineering, Technical University of Denmark, DK-2800, Lyngby, Denmark

A R T I C LE I N FO A B S T R A C T

Keywords: The effect of post-manufacture heat-treatment on the mechanical strength of an additively-manufactured aus-
Additive manufacturing tenitic stainless steel has been investigated. Microstructural investigations revealed that the as-manufactured
316L stainless steel material exhibited a multi-scale structure, composed of grains, cells, dislocations and nano-sized particles.
Heat-treatment Annealing at 400°C resulted in a 10% increase in yield strength, associated with the additional precipitation of a
Mechanical properties
population of nano-sized silicates. Annealing at higher temperatures resulted in a decrease in strength, attributed
Orowan strengthening
primarily to the thermal instability of the cell structure in the as-manufactured material. The results demonstrate
that by careful control of annealing conditions the structure and mechanical properties of additively-manu-
factured austenitic stainless steel can be optimized by post-manufacture heat-treatment.

1. Introduction the mechanical properties and performance of additively-manufactured

components can also be modified by post-manufacture heat-treatment.
Additive manufacturing (AM) is a rapidly developing technology, For example, the occurrence of phase transformations has been re-
combining computer-aided design with material processing and ported in additively-manufactured 316L SS after annealing at high
forming to allow the creation of solid objects [1–10]. Among the var- temperature [4]. A key point, however, is that the high strength and
ious AM methods, selective laser melting (SLM) is of increasing interest good ductility of additively-manufactured 316L SS has been attributed
for the manufacture of engineering materials. In this method a high- in part to the presence of a dislocation network structure [12]. As an-
energy laser beam is used to melt locally a bed of metal powder ac- nealing at elevated temperatures can result in a reduction in dislocation
cording to a pre-determined design, resulting in the manufacture of a density via thermally-activated recovery processes, this may therefore
two-dimensional cross-section [8–10], with solid parts achieved by re- result in a deterioration in mechanical properties. Accordingly, it is
peating this process layer-by-layer from bottom to top to form the final necessary to study carefully the link between the thermal stability of the
part [8,11]. This “bottom-up” AM method allows the production of dislocation network structure and changes in mechanical properties
complex structural parts that cannot be achieved by traditional pro- during annealing of additively-manufactured 316L SS.
cessing methods.
316L stainless steel (316L SS) is an austenitic composition with high 2. Experimental
strength and good corrosion resistance, widely used in the aerospace,
energy, and automotive industries, as well as in medical devices [3,8]. The material used in this study is an additively-manufactured 316L
Due both to its relatively high machining costs, and to its high sensi- SS, produced by the SLM method. Detailed information regarding the
tivity to grain boundary corrosion after welding, there is increasing material is given in Ref. [12]. Samples for investigation were cut by
interest in the manufacture of 316L SS parts by AM, through which spark machining, mechanically polished, and then annealed for 1 h at
near-net-shape components can be produced. various temperatures up to 800°C, followed in each case by water
In addition to optimization of the process parameters during AM, cooling.

☆
The authors declare that this work is our original studies; the work has not been published and is not under consideration for publication elsewhere.
∗
Corresponding author.
E-mail address: [email protected] (G. Wu).

https://doi.org/10.1016/j.msea.2019.04.111
Received 11 January 2019; Received in revised form 28 April 2019; Accepted 29 April 2019
Available online 30 April 2019
0921-5093/ © 2019 Elsevier B.V. All rights reserved.
N. Chen, et al. Materials Science & Engineering A 759 (2019) 65–69

Micro-hardness was measured using a load of 1 kg and a dwell time Fig. 3 shows TEM images of the as-manufactured sample and of
of 10 s. Ten measurements were performed on each sample. Dog-bone samples annealed at 400°C and 800°C for 1 h. As shown in Fig. 3(a) and
shaped tensile specimens with a gauge size of 8 mm in length, 2 mm in (b), a characteristic cell structure is seen in the as-manufactured
width and 1 mm in thickness, were cut with the tensile axis perpendi- sample, similar to that seen previously in additively-manufactured 316L
cular to the build direction. The samples were tested at a constant strain SS [6,12]. In some regions cellular sub-grains are observed (Fig. 3(a)),
rate of 4 × 10−4 s−1. whereas other regions are composed of columnar sub-grains (Fig. 3(b))
Microstructural characterization was carried out using an Oxford [7]. The average cell diameter, as determined from TEM images
AZtec electron backscattered diffraction (EBSD) detector attached to a showing cells with an equiaxed morphology, is about 0.48 μm (see
JEOL 7800F scanning electron microscope (SEM), and a JEOL 2100 Table 1), with a columnar length of more than 10 μm. Many disloca-
transmission electron microscope (TEM). Samples for EBSD were me- tions are also observed within the cells (see Fig. 4).
chanically polished followed by electropolishing at 20 V for 10 s in an After annealing at 400°C for 1 h, both the cell structure and the high
electrolyte of perchloric acid and acetic acid (1:4 ratio) at room tem- density of cell-interior dislocations are preserved (Figs. 3(c) and 2(d)),
perature (RT). Analysis of the EBSD data was carried out using the with almost no detectable change in the average cell diameter (see
Oxford Instruments Channel 5 software package. Specimens for TEM Table 1). The characteristic cell structure of the as-manufactured
investigation were ground to approximately 50 μm thickness, and then sample is therefore thermally stable at temperatures up to 400°C.
thinned by jet-polishing using a voltage of 50 V at −20°C in an 5% However, after annealing at 800°C for 1 h (Fig. 2(e) and (f)), a sig-
perchloric acid/ethanol solution. The chemical composition was ana- nificant change in the dislocation structure is observed, with the mi-
lyzed using energy-dispersive X-ray spectroscopy (EDS) in a FEI crostructural appearance changing to be more typical of that seen in
TECNAI G2 F20 TEM. 316L SS after plastic deformation at elevated temperatures [13]. In-
terestingly, however, the length scale of the dislocation cell structure
3. Results and discussion remains almost unchanged.
Inspection of the TEM images also reveals that a randomly dis-
Fig. 1(a) shows the micro-hardness of the additively manufactured tributed population of nano-sized particles is present in the. Further
316L SS as a function of heat-treatment temperature. The micro-hard- investigation shows that the number of particles increases significantly
ness of the as-manufactured material is 252 HV. With increasing an- after annealing 400°C for 1h. EDS measurements indicate that these
nealing temperature, the micro-hardness first gradually increases to a particles are Si-O-Mn silicates. Results of EDS mapping for a typical
maximum value of 291 HV at 400°C, and then continuously decreases region in the 400°C annealed sample are shown in Fig. 4. Similar sili-
to 228 HV at 800°C. Fig. 1(b) shows tensile curves of the as-manu- cates have been reported in additively-manufactured 316L SS [3-5,12-
factured sample and of samples annealed at 400°C and 800 °C for 1 h. 14], in agreement with the present results and indicating a similar
The yield strength and uniform elongation in the as-manufactured mechanism for the formation of these silicates. For each sample five
condition are 586 MPa and 35%, respectively. After annealing at 400°C areas were characterized using the TEM observations to determine both
for 1 h, the yield strength increases to 642 MPa, while the uniform the volume fraction and average size of silicates. The results are listed
elongation only slightly decreases to 32%. After annealing at 800°C for in Table 1. It is seen that in the as-manufactured sample the volume
1 h, the yield strength decreases to 482 MPa and the uniform elongation fraction of silicates is only 0.42%, and that these silicates have a rela-
is restored to 35%. tively large average size. After annealing at 400°C for 1 h, the volume
Fig. 2 shows example EBSD orientation maps of the as-manu- fraction of silicates increases to 1.36%, indicating that precipitation of
factured sample and of samples annealed at 400°C and 800°C for 1 h. silicates takes place during annealing at 400°C. The newly precipitated
The EBSD maps reveal a microstructure typical of additively-manu- silicates are small in size, resulting in a decrease in the average silicate
factured material, namely a checkerboard macrostructure in the section particle size. After annealing at 800°C, some dissolution of the silicates
perpendicular to the build direction (as shown in Fig. 2(a–c)), and a takes place, resulting in a decrease in the volume fraction to 0.61%,
columnar grain structure in sections containing the build direction (as accompanied by a small decrease in the average particle size.
seen in Fig. 2(d–f)) [12]. This microstructural appearance has been The contribution to the tensile yield strength of the silicates (Δσ) can
attributed to rapid melting and solidification away from equilibrium be estimated according to the Orowan mechanism, as described by:
conditions during the AM process [4,12]. Grain sizes were determined G⋅b
from the EBSD maps using an area reconstruction method with a 2° Δσ = M⋅Δτ = M⋅
λ (1)
grain boundary definition, and are given in Table 1 as equal circular
diameter values. The average grain size in the as-manufactured sample where M is the Taylor factor, τ the shear stress, G the shear modulus, b
is about 5.9 μm, with only a small variation observed after annealing at the Burgers vector, and λ the average spacing of the silicate particles.
either 400°C or 800°C. Here, λ is determined using the equation:

Fig. 1. (a) Micro-hardness of additively-manufactured 316L SS after annealing at various temperatures for 1 h; (b) engineering stress-strain curves of the as-
manufactured 316L SS sample and of samples annealed at 400°C and 800°C for 1 h.

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N. Chen, et al. Materials Science & Engineering A 759 (2019) 65–69

Fig. 2. EBSD orientation maps of the as-manu-

factured sample (a, b), and of samples annealed at
400°C (c, d) and 800°C (e, f) for 1 h. The micro-
structure in the section taken perpendicular to the
build direction is shown in (a, c, e), while (b, d, f)
show a section containing the build direction. White
lines represent misorientations ≥ 2° and < 15°, with
black lines showing misorientations ≥15°.

Table 1 particles. Based on these equations, and using the values given in
Microstructural parameters and calculated Orowan strengthening contribu- Table 1, the strength contributions due to the silicate particles have
tions. been estimated, taking values of M = 3.06, G = 77.2 GPa and
Sample as-manufactured 400°C/1 h 800°C/1 h b = 0.256 nm. The results are given in Table 1. It is seen that the silicate
particles contribute very little to the yield strength of the as-manu-
Average grain size, μm 5.9 5.6 5.4 factured sample, due both to their small volume fraction and the large
Average cell diameter, μm 0.48 0.50 0.46
average particle size. However, in the sample annealed at 400°C for 1 h
Volume fraction of particles (f), % 0.42 1.38 0.61
Average particle size (d), nm 64 21 14 the newly precipitated silicates contribute about 55 MPa to the yield
Average particle spacing (λ), μm 10.1 0.97 1.49 strength – almost completely accounting for the increase in strength of
Orowan strengthening (Δσ), MPa 6 61 40 the as-manufactured sample after annealing at this temperature
(56 MPa).
Interestingly, based on the microstructural parameters the silicate
4(1 − f ) r
λ= particles are predicted to give a strength contribution of 34 MPa after
3f (2) annealing at 800°C for 1 h. Annealing at 800°C for 1 h in fact results,
however, in a decrease of the yield strength of 104 MPa compared to
where f is the volume fraction, and r is the average radius of the silicate

Fig. 3. TEM images of the as-manufactured sample (a, b), and of samples annealed at 400 °C (c, d) and 800 °C (e, f) for 1 h. Examples of cell structures are shown in
micrographs (a), (c) and (e), while examples of columnar structures are shown in (b), (d) and (f).

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Fig. 4. Example EDS mapping showing the presence of silicates in the sample annealed at 400 °C for 1 h. (a) TEM image; (b), (c), (d), (e) and (f) are element
distribution maps of Fe, Cr, Si, O and Mn, respectively.

the as-manufactured sample. Moreover, the length scale of the dis- strength. However, annealing at higher temperatures leads to a con-
location cell structure in this condition is comparable to that of both the tinuous decrease in micro-hardness and yield strength, despite the
as-manufactured sample and of the sample annealed at 400 °C for 1 h continued presence of a population of silicate particles, suggesting that
(as seen in Table 1). The appearance of the cell structure is, however, at temperatures higher than 400°C a transformation of cell/dislocation
very different in the sample annealed at 800 °C, indicating that at this structure take place, resulting in a reduced strength contribution. This
temperature significant modifications to the dislocation arrangements conclusion is supported by the observation of a change in the appear-
forming the cell structure have taken place. ance of the cell structure in the sample annealed at 800 °C.
These observations highlight the importance of preserving the dis-
location cell structure of the as-manufactured material during any 4. Conclusions
subsequent heat-treatment, and shows additionally that a window of
annealing temperatures exists where the cell structure can be preserved The microstructural stability and mechanical properties of addi-
while also taking advantage of other strengthening mechanisms. The tively manufactured 316L SS during post-manufacture heat treatment
exact origin of the strength contribution from the dislocation cell have been studied by annealing at temperatures up to 800°C for 1 h.
structure is not yet fully understood, and further studies to examine the Annealing at temperatures up to 400°C leads to an 10% increase in yield
specific changes in the dislocation arrangements in the cell structure strength compared to the as-manufactured state, from 586 MPa to
that take place during annealing are necessary. 642 MPa, with only a small loss in uniform elongation. This is attributed
A consideration that should be taken into account in this regard is to the thermal stability of the cell/dislocation structure, in combination
that annealing of 316L SS may introduce sensitization of the grain with precipitation of nano-sized silicate particles. The preservation of
boundaries. A preliminary study has shown, for example, that rapid the cell/dislocation structure allows the high strength and good ducti-
attack on the boundaries of melting pools in additively manufactured lity of the as-manufactured material to be maintained, while the sili-
316L SS may occur after annealing at 650 °C for 1 h [15]. Therefore, it is cates contribute via an Orowan mechanism to the majority of the ob-
also important to study the consequence of annealing on the corrosion served strength increase of 56 MPa in the sample annealed at 400 °C for
behavior of additively manufactured 316L SS, even for low-carbon 1 h. Annealing at temperatures higher than 400°C results, however, in a
compositions that are traditionally considered as resistant to sensiti- continuous decrease in the strength of the material, as the cell structure
zation. Preliminary oxalic acid tests according the ASTM A262 Practice is no longer stable, and some dissolution of the silicates takes place.
A [16] on the 316L SS material of this study show no sensitization of The present study shows that by careful control of the annealing
grain boundaries of the present as-manufactured and of the 800 °C conditions the mechanical properties of additively-manufactured 316L
annealed samples [see supplementary material]. SS can be further increased by post-manufacture heat treatment, pro-
The results of the present study show that additive manufacturing of viding a route for enhancement in mechanical properties of additively-
316L SS results in a multi-scale structure. On the melt pool scale, a manufactured 316L SS parts in addition to optimization of the AM
checkerboard pattern is formed, consisting of grains with size of up to processing parameters. The results also highlight the importance of
tens of micrometers, separated in many cases by high angle boundaries. understanding the strength contribution and thermal stability of the cell
Inside these grains, a cell structure is developed, where the average cell structure formed during additive manufacturing, and how these relate
size is a few hundred nanometers. Within these cells, a high density of to the nature of the dislocation arrangements in the as-manufactured
dislocations and a population of nano-sized silicate particles are found. and annealed conditions. Although the results presented here are for
This multi-scale structure results in a yield strength of the as-additively 316L SS, the findings of the present study can be also applied to other
manufactured 316L SS of 586 MPa, very close to that reported else- heat-treatable metallic materials produced using additive manu-
where [6,12]. During annealing at temperatures up to 400°C fine sili- facturing, thus pointing to a new avenue for tailoring the mechanical
cate particles are precipitated, while the cell structure and dislocations properties of additive-manufactured parts by controlled heat-treat-
are stable. This results in a gradual increase in micro-hardness and yield ments.

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