RESEARCH AND EDUCATION

Oriented face-centered cubic to hexagonal close-packed

martensitic transition, grain morphology, and mechanical
properties of Co-Cr alloy fabricated by selective laser melting
Xiang Yan, MDS,a Ruodan Jiang, MS,b Wen Li, MS,c and Hong Lin, DDS, PhDd

Removable partial dentures ABSTRACT

(RPDs) have typically been
Statement of problem. Removable partial dentures (RPDs) can be fabricated by selective laser
made from cobalt-chromium melting (SLM) with different build orientations. How microstructures and mechanical properties
(Co-Cr) alloys; however, the of SLM Co-Cr alloy are affected by different build orientations is unclear.
conventional lost-wax casting
Purpose. The purpose of this in vitro study was to investigate the phase structures, grain
process for RPD frameworks is
morphology, and mechanical properties of SLM Co-Cr alloy with different build orientations.
complex, and obtaining an
accurately fitting prosthesis Material and methods. SLM Co-Cr tensile specimens were fabricated at orientation angles of 0, 45,
1
challenging. Recently, selec- and 90 degrees between the building and longitudinal direction named the T0, T45, and T90 design
groups (n=14). Mechanical properties were obtained by tensile testing conducted by using a
tive laser melting, a metal-
universal testing machine according to the International Organization for Standardization (ISO)
based 3D printing technique, 22674. The grains along the longitudinal direction of the specimens and phase structures were
has facilitated the production observed before and after tensile testing by electron backscatter diffraction. One-way analysis of
of RPDs with remarkable cost variance followed by the Bonferroni post hoc test and Kruskal-Wallis test were used for statistical
savings.2-5 Co-Cr alloys are analysis (a=.05).
popular SLM dental materials Results. The 0.2% yield strengths in descending order were T90 (870 MPa)>T45 (840 MPa)>T0 (786
because of their good MPa) (P<.05); the elongations were T0 (21.8%)>T45 (15.6%)>T90 (8.7%) (P<.05); the ultimate tensile
biocompatibility, low cost, and strengths were T45 (1226 MPa)>T90 (1200 MPa)>T0 (1149 MPa) (P<.05). The average grain sizes in
straightforward 3D printing.2-6 the T0, T45, and T90 groups were 22 mm, 18 mm, and 14 mm, respectively. After the tensile test, a
Studies have also shown that face-centered cubic (FCC) to hexagonal close-packed (HCP) martensitic transition was found in each
prostheses fabricated with group, and the phase transition area fractions were T0 (38.3%)>T45 (11.4%)>T90 (0.7%).
SLM Co-Cr alloys have better Conclusions. The FCC to HCP martensitic transition, grain morphology, and mechanical properties
corrosion resistance and of SLM Co-Cr alloy depended on the build orientations. The oriented phase transition and grains
higher strength compared with affected the anisotropic mechanical properties of SLM Co-Cr alloy. (J Prosthet Dent 2022;127:282-7)
those fabricated with conven-
tional casting methods.7-9 microstructures of the SLM Co-Cr alloys should be
With the SLM process, the RPD frameworks can be determined as a function of the build orientation. How-
printed on the metal substrate in different build orien- ever, studies on this subject are sparse. Two studies have
tations (Fig. 1), and the mechanical properties and reported that the mechanical properties of the SLM

Supported by the National Key Research and Development Program of China (Grant number 2018YFB1106905).
a
Assistant, Department of Dental Materials Laboratory, Hospital of Stomatology, Peking University, Beijing, PR China.
b
Engineer, Department of Dental Materials Laboratory, Hospital of Stomatology, Peking University, Beijing, PR China.
c
Engineer, Department of Dental Materials Laboratory, Hospital of Stomatology, Beijing, PR China.
d
Professor and Director, Department of Dental Materials Laboratory, National Medical Products Administration Key Laboratory for Dental Materials & Dental Medical Devices
Testing Center, Peking University School of Stomatology, Beijing, PR China.

282 THE JOURNAL OF PROSTHETIC DENTISTRY

February 2022 283

Clinical Implications
SLM Co-Cr alloys have oriented microstructures and
mechanical properties that indicate SLM RPD
frameworks with a specific build orientation should
satisfy clinical requirements.

Co-Cr alloy depend on the build orientations,10,11 but

specific details were lacking. Figure 1. Removable partial denture frameworks with different build
The strength and ductility of Co-Cr alloys depend on orientations.
the face-centered cubic (FCC) and hexagonal close-
packed (HCP) crystal phases.10,11 The FCC structure
provides ductility because of easier dislocation motion; by
contrast, the HCP phase is more brittle because of its
limited capacity for dislocation motion.12-14 Furthermore,
the strain-induced martensitic transformation (SIMT) of
the FCC phase can occur in Co-based alloys with low
stacking fault energy, which can significantly affect the
mechanical behavior of the alloy.14-16 The SIMT can
induce plasticity, which can increase the strength of al-
loys.15,16 In addition, grain morphology can also have
significant effects on the mechanical properties of
alloys.17,18
The purpose of this in vitro study was to investigate
the phase structures, grain morphology, and mechanical
properties of SLM Co-Cr alloy with different build ori-
Figure 2. Island laser scanning strategy.
entations. The null hypotheses were that the FCC to
HCP martensitic transition, grain morphology, and me-
to ISO 22674.19 The 0.2% yield strengths (s0.2) and
chanical properties of the SLM alloy would not depend
ultimate tensile strength (UTS) were obtained from the
on the build orientation.
stress-strain curves of the specimens, and the elonga-
tions were determined with the fractured pieces fitted
MATERIAL AND METHODS
together microscopically, which was in compliance with
The Co-Cr alloy powder (Dental Co-Cr alloy powder; ISO 22674.19
Upcera) with a weight percentage composition of Co Before and after tensile testing, 2 specimens in every
62%, Cr 25%, Mo 6%, W 5%, Si 1%, Mn 1%, Fe<1.0% group were prepared to observe the phase structure and
was used in this study, and the particle sizes of 90% alloy grains by electron backscatter diffraction (EBSD). In order
powder were within 80 mm. The SLM machine (FS121M- to prepare EBSD test specimens, cylinders with a height
D; Farsoon) was used to prepare the specimens under a of 5 mm were formed by cutting along the middle of the
nitrogen atmosphere; the laser spot diameter was 76 mm; tensile specimen before and after tensile testing. Then 1.0
the laser power was 200 W; the scan speed was 15.2 m/s; mm was wet ground from the side of the cylinders by
and the layer thickness was 0.03 mm. With the SLM using 240-, 400-, 600-, 800-, 1000-, 1200-, and 2000-grit
process, the island laser scanning strategy was used as Al2O3 abrasive paper. Finally, the specimens were pol-
illustrated in Figure 2. As shown in Figure 3, the tensile ished with an electrolyte consisting of glycol and sulfuric
specimens prepared in compliance with the International acid for Co-Cr alloy (megalyt; megadental); the electro-
Organization for Standardization (ISO) 2267419 were lytic voltage was 220 V; the electrolytic current intensity
designated according to the 0-, 45-, and 90-degree build was 16 A; and the electrolytic time was 8 minutes. The
orientations and built up with the longitudinal axes in- EBSD observations were performed in the long axis di-
clined from the build direction by 0-, 45-, and 90- rection (Fig. 4) of the specimens before (near the center)
degrees, namely the T0, T45, and T90 groups. and after the tensile test (near the specimen fracture) at a
Fourteen specimens in each group were used for step size of 1.5 mm by using an SEM (S-3400 N; Hitachi)
uniaxial tensile testing. The tensile testing was conducted equipped with an EBSD system (AZtec EBSD; Oxford
in air at 25  C by using a universal testing machine (3367; Instruments). Based on the EBSD technology, boundary
INSTRON) at a cross-head speed of 2 mm/min according segments with a critical orientation difference angle

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284 Volume 127 Issue 2

Figure 4. Electron backscatter diffraction observation position.

Figure 3. Selective laser melted tensile specimens with different build Table 1. Mechanical properties
orientations. A, T0; B, T45; C,T90.
Groups s0.2 (MPa) UTS (MPa) Elongation (%)
T0 786 ±26.2 1149 ±28.1 21.8 ±3.19

higher than 10 degrees were identified and defined as T45 840 ±39.6 1226 ±26.3 15.6 ±2.66
T90 870 ±26.1 1200 ±23.7 8.7 ±1.06
grain boundaries. The EBSD data were collected and
T0 and T45 P<.001 P<.001 P<.001
analyzed by using a software package (HKL Channel 5;
T0 and T90 P<.001 P<.001 P<.001
Oxford Instruments). The experimental data were eval-
T45 and T90 P=.046 P=.035 P<.001
uated with 1-way analysis of variance (ANOVA) followed
s0.2, 0.2% yield strength; UTS, ultimate tensile strength.
by the Bonferroni post hoc test with a statistical software
program (IBM SPSS Statistics, v24.0; IBM Corp) and the
Kruskal-Wallis test (a=.05).
The EBSD phase map (Fig. 6) indicates that the tested
RESULTS regions of the specimens before the tensile test consisted
of a single FCC phase without an HCP phase. However,
As can be seen from Table 1, the order from the highest
after the tensile test, the HCP phase was found in all of
to lowest s0.2 values of the test specimens was
the specimens, and in the order from the highest to
T90>T45>T0. The variability of s0.2 values among the 3
lowest HCP phase area fractions in tested regions of the
groups was homogeneous (df1=2; df2=39; P=.221). One-
specimens were T0 (38.3%)>T45(11.4%)>T90 (0.7%).
way ANOVA analysis revealed a significant difference in
These indicated that the FCC to HCP martensitic trans-
the s0.2 (df1=2; F=25.823; P<.05), and the Bonferroni post
formation occurred during the tensile test. In addition,
hoc test demonstrated significant differences among the
the HCP phase texture direction of T0 and T45 were
groups (P<.05). The order of the UTS values was
identical to the corresponding build orientation.
T45>T90>T0. As a result of homogeneous variability
(df1=2; df2=39; P=.137), the 1-way ANOVA analysis re-
DISCUSSION
vealed a significant difference in the UTS results in the 3
groups (df1=2; F=31.661; P<.05), and the Bonferroni post The ductility and strength of the SLM Co-Cr alloys tested
hoc test showed significant differences among the groups depended on the build orientation and exceeded the
(P<.05). The elongation values were T0>T45>T90, while requirements of ISO 2267419 for the V type alloy
the variability among the 3 groups was inhomogeneous (s0.2 500 MPa, elongation 2 %) used for thin metal
(df1=2; df2=39; P<.001). The Kruskal-Wallis test showed RPD, frameworks. Furthermore, clear distinctions were
significant differences in the elongation values among found in the grain morphology and FCC to HCP trans-
the groups (P<.05). formation in the T0, T45, and T90 groups. Therefore, the
Figure 5 shows the grain morphologies and low-angle null hypothesis was rejected.
grain boundaries (LAGBs, <15 degrees), where it can be Variations in grain shapes among the 3 groups were
seen that the long axis of the grains and grain boundaries clear in the microscopic observations (Fig. 5). Because of
of T0 and T45 were the same as the corresponding build the directional solidification during the SLM process, the
orientations. In addition, the grain overall morphology of grains of the T0 and T45 groups extended and stacked
T90 was similar for different scanning strategies. The along the build orientations, creating aligned grain
mean values and standard deviations of the grain sizes in structures and larger grain sizes than T90 along the build
the T0, T45, and T90 groups were 22 ±23 mm, 18 ±16 mm, orientations. The tested surface of T90 was perpendicular
and 14 ±12 mm, respectively. Moreover, group T90 to the build direction, and its grain overall morphology
showed that the LAGBs were mainly located in the was similar to islands or a chessboard, reflecting the
crisscrossing regions of the island laser scanning strategy, characteristics of the scanning strategy. When the di-
where the grain sizes were smaller. Compared with T0 rection of shear stress is consistent with or close to the
and T45, the LAGBs of T90 were denser. grain boundary, the probability of dislocation blocking

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February 2022 285

orientation and the 3D dimensions of theses grains were

unclear. The LAGBs pose a major obstacle to dislocation
penetration, and the interaction of dislocations with
LAGBs has been shown as a substantial contribution to
the strength of metals.20,21 Therefore, the differences of
LAGBs in the 3 groups should also contribute to the
differences of their yield strengths.
The FCC phase is stable at high temperatures, while
the HCP phase exists as an equilibrium phase at lower
temperatures.13,16,22 The equilibrium phase diagram of
Co-Cr alloys indicates that at >900  C, the expected
structure is the FCC structure and that at <900  C, it is
the HCP structure.23-25 Under the thermodynamic con-
ditions of below or about 900  C, accompanied by the
diffusion of alloy elements, the diffusional FCC to HCP
martensitic transformation occurs slowly in Co-Cr
alloy.23-25 In addition, because of a low stacking fault
energy, the FCC to HCP martensitic transformation
during plastic deformation at room temperature also
occurs because of shear of 1/6 <1210> on {111}fcc planes,
referred to as the SIMT.14-16,26
With the SLM process, rapid cooling of the specimen
suppresses the FCC to HCP transition; consequently, the
FCC structure is dominant in the as-built SLM Co-Cr
alloy.10,11,23,24,27 After the tensile test, the HCP struc-
ture was present, which indicated that the SIMT with
FCC to HCP transformation occurred during the tensile
test. Furthermore, this induced martensitic trans-
formation can also increase plasticity.28 Under tensile
stress, the FCC to HCP transformation causes stress
relaxation in the specimen and gives rise to a uniform
deformation in the SLM Co-Cr alloy instead of necking
behavior, which leads to high UTS and high plasticity.28
In the present study, the FCC to HCP transformation
of the SLM Co-Cr alloy depended on the build orienta-
tion, and the experimental results revealed that the area
percentages of FCC to HCP transformation in the tested
area of T0, T45, and T90 were 38.3%, 11.4%, and 0.7%,
respectively. Therefore, in the order of highest to lowest
ductility, the specimens were T0>T45>T90. Furthermore,
the yield strengths of T45 were lower than those of T90,
but it had higher ultimate tensile strengths, which may
be attributed to this phase transition. During the FCC to
HCP transition, the 2 structures should follow the
orientation relationship of {111}fcc ||{0001}hcp based on
the gliding of the partial dislocation of 1/6 <1210> in
Figure 5. Grain morphologies. A, T0; B,T45; C, T90. Original every second {111}fcc plane.14-16,26 The orientation rela-
magnification ×250. LAGBs, low-angle grain boundaries (LAGBs, <15 tionship probably resulted in the phase transformation of
degrees) SLM Co-Cr alloy depending on the build orientation;
however, the mechanism should be further studied.
has been reported to decrease, resulting in lower yield Cast Co-Cr alloy typically exhibits isotropic micro-
strength.17 In the present study, the order of largest to structures and mechanical properties. However, casting
smallest grain size was T0>T45>T90; however, these defects such as pores are unavoidable and reduce the
grains were observed on 2D surfaces of specimens, ductility and strength of dental Co-Cr RPD frameworks.
mainly reflecting the 2D dimensions of grains in the build The present study highlights that the microstructures of

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286 Volume 127 Issue 2

Figure 6. Phase structures. A, T0; B, T0 after tensile test.; C, T45; D, T45 after tensile test; E, T90; F, T90 after tensile test. Original magnification ×250. FCC,
face-centered cubic; HCP, hexagonal close-packed.

the Co-Cr alloy fabricated using SLM have unique grain restorations with different build orientations require
morphologies and FCC to HCP phase transformation, increased attention that can lead to further understand-
thereby improving the ductility and strength of the alloy. ing when SLM Co-Cr frameworks are used in clinical
In addition, the differences between the mechanical applications. SLM Co-Cr alloys have oriented micro-
properties and microstructure of SLM Co-Cr alloy structures and mechanical properties indicating that the

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February 2022 287

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