Accepted Manuscript

Full length article

Novel β-Ti35Zr28Nb alloy scaffolds manufactured using selective laser melting

for bone implant applications

Yuncang Li, Yunfei Ding, Khurram Munir, Jinxing Lin, Milan Brandt, Andrej
Atrens, Yin Xiao, Jagat Rakesh Kanwar, Cuie Wen

PII: S1742-7061(19)30073-X
DOI: https://doi.org/10.1016/j.actbio.2019.01.051
Reference: ACTBIO 5907

To appear in: Acta Biomaterialia

Received Date: 12 October 2018

Revised Date: 21 January 2019
Accepted Date: 24 January 2019

Please cite this article as: Li, Y., Ding, Y., Munir, K., Lin, J., Brandt, M., Atrens, A., Xiao, Y., Kanwar, J.R., Wen,
C., Novel β-Ti35Zr28Nb alloy scaffolds manufactured using selective laser melting for bone implant applications,
Acta Biomaterialia (2019), doi: https://doi.org/10.1016/j.actbio.2019.01.051

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 Novel β-Ti35Zr28Nb alloy scaffolds manufactured using selective laser
melting for bone implant applications
Yuncang Li1,*, Yunfei Ding1,2, Khurram Munir1, Jinxing Lin3, Milan Brandt1, Andrej Atrens4,

Yin Xiao5, Jagat Rakesh Kanwar6, Cuie Wen1,*

1
School of Engineering, RMIT University, Melbourne, Victoria 3001, Australia
2
School of Mechanical Engineering, Huaihai Institute of Technology, Lianyungang, Jiangsu
222005, China
3
Advanced Material Research and Development Center, Zhejiang Industry & Trade
Vocational College, Wenzhou, Zhejiang 325003, China
4
School of Mechanical and Mining Engineering, The University of Queensland, St Lucia,
Queensland 4072, Australia
5
Institute of Health and Biomedical Innovation, Queensland University of Technology,
Brisbane, Queensland 4059, Australia
6
Faculty of Health, School of Medicine, Deakin University, Waurn Ponds, Geelong, Victoria
3217, Australia

*Corresponding Author:
Yuncang Li, Associate Professor
School of Engineering
RMIT University, Melbourne, Victoria 3001, Australia
Tel.: +613 9925 7560, Fax: +613 9925 6108
E-mail: [email protected]

Cuie Wen, Distinguished Professor

School of Engineering
RMIT University, Melbourne, Victoria 3001, Australia
Tel.: +613 9925 7290, Fax: +613 9925 6108
E-mail: [email protected]
Abstract

Titanium (Ti) based tissue engineering scaffolds can be used to repair damaged bone.

However, successful orthopedic applications of these scaffolds rely on their ability to mimic

the mechanical properties of trabecular bone. Selective laser melting (SLM) was used to

manufacture scaffolds of a new β-Ti35Zr28Nb alloy for biomedical applications. Porosity

values of the scaffolds were 83% for the FCCZ structure (face centered cubic unit cell with

longitudinal struts) and 50% for the FBCCZ structure (face and body centered cubic unit cell

with longitudinal struts). The scaffolds had an elastic modulus of ~1 GPa and a plateau

strength of 8-58 MPa, which fall within the values of trabecular bone (0.5~5 GPa for elastic

modulus and 4~70 MPa for compressive strength). The SLM-manufactured β-Ti35Zr28Nb

alloy showed good corrosion properties. MTS assay revealed that both the FCCZ and FBCCZ

scaffolds had a cell viability similar to the control. SEM observation indicated that the

osteoblast-like cells adhered, spread and grew healthily on the surface of both scaffolds after

culture for 7, 14 and 28 d, demonstrating good biocompatibility. Overall, the SLM-

manufactured Ti35Zr28Nb scaffolds possess promising potential as hard-tissue implant

materials due to their appropriate mechanical properties, good corrosion behavior and

biocompatibility.

Keywords: β-titanium alloy; biocompatibility; corrosion; mechanical property; selective laser

melting.
1. Introduction

Titanium (Ti) and Ti-based alloys such as Ti6Al4V (Ti64) and Nitinol (NiTi) have been used

extensively as orthopedic biomaterials due to their good mechanical properties, good

corrosion behavior, and biocompatibility [1-4]. However, toxic-metal ion release from Ti-

alloy implants is of possible concern, as this can cause biological harm or elicit an allergic

reaction. For example, vanadium (V) and aluminum (Al) are potentially cytotoxic, and Ti64

can produce adverse reactions in the human body [5-7]. Humans can suffer an allergy and

cancer associated with nickel (Ni) [8, 9]. Furthermore, concerns also remain regarding the

elastic modulus of Ti-alloys, which is higher than that of natural bone [10, 11] and so may

cause stress shielding that leads to loosening of the implant and premature failure [12, 13].

Consequently, biocompatible β stabilizing alloying elements such as molybdenum (Mo),

niobium (Nb), silicon (Si), tantalum (Ta), tin (Sn) and zirconium (Zr) are being explored to

develop new biocompatible β-Ti alloys because the β-Ti alloys can exhibit a lower elastic

modulus compared to α and α+β Ti alloys [2, 11, 14-17]. New β-Ti–Nb–Zr (TNZ) alloys

(Ti25Zr34Nb, Ti32Zr30Nb, Ti35Zr28Nb, and Ti40.7Zr24.8Nb) were recently developed [16].

These β-TNZ alloys display excellent cytocompatibility and desirable mechanical properties,

such as a high admissible-elastic strain (the ratio of yield strength to elastic modulus) and

considerable ductility with no cracking or fracture during compression tests. In particular, the

Ti35Zr28Nb alloy showed an elastic admissible strain of 1.31%, significantly higher than that

of grade 4 pure Ti (0.47%) and mill-annealed Ti64–ELI (0.80%) [16].

Ti alloys with open-cell porosity exhibit values of elastic modulus lower than bulk Ti alloys

[12, 18]. The open-cell pores provide space for new bone tissue ingrowth and vascularization

[19-23]. A number of Ti alloys with porous structures mimicking that of natural bone have

been developed using conventional methods such as powder metallurgy, melt gas injection,
foaming agent decomposition in metal melts, gas–metal eutectic solidification, and

entrapped-gas expansion [11, 24-26]. However, conventional manufacturing processes may

manufacture porous metals with stochastic defects such as relatively poor uniformity, low

manufacturable geometric complexity, and restricted achievable mechanical properties,

leading to limitations in achieving controlled porosity, porous characteristics, and controlled

mechanical properties for bone implant applications [27-29].

Additive manufacturing (AM) techniques such as electron beam melting (EBM) [30] and

selective laser melting (SLM) [31] have enabled the successful production of open-cell metal

scaffolds for biomedical applications. AM techniques exhibit a number of advantages over

conventional manufacturing processes, such as precise control of porosity, pore size, shape,

and geometry, and the capability to manufacture complex, patient-specific components [30-

35]. SLM and EBM progressively build up scaffolds using a scanning laser beam or an

electron beam to selectively melt subsequent layers of metal powder in an inert gas

atmosphere, respectively [30, 31, 36]. Prior studies have focused on fabricating scaffolds of

commercially pure Ti (CP-Ti) and Ti64 using SLM and EBM, for biomedical applications

[30, 31, 35, 37-40]. SLM-manufactured CP-Ti and Ti64 alloys have microstructures of α or

α+β phases [33, 34]. To date, there have been few studies on fabricating β Ti alloy scaffolds

using SLM and EBM. Furthermore, AM is a complex and multi-physics process, which is

subject to processing limitations. There are many variables that influence the quality of the

final product, such as large thermal gradients, complex geometries, local overheating, local

heat transfer paths, and thermal powder bed resistance [30, 31, 41-43], which necessitate new

research in the fabrication of β Ti alloy scaffolds by AM.

This study develops the β-Ti35Zr28Nb alloy in both bulk and porous forms by SLM. The

SLM processing parameters are determined by experimental evaluation. Bulk and porous

samples are fabricated by SLM, and their microstructures, mechanical properties, corrosion
behavior, and in vitro biocompatibility are assessed for bone implant applications, such as

craniomaxillofacial implants, spine fusion cages and dental implants.

2. Materials and methods

2.1 Ti35Zr28Nb scaffold samples

An as-cast Ti35Zr28Nb alloy ingot was prepared using a consumable-electrode vacuum arc

furnace melting method. The ingot was atomized into spherical powder using a plasma

rotating electrode atomization system. Fig. 1 presents the size distribution and morphology of

the Ti35Zr28Nb alloy powder. Both bulk and porous samples were fabricated using an SLM

machine (SLM Solutions 125HL, Germany). Table 1 presents the compositions of the

Ti35Zr28Nb alloy powder and the SLM-manufactured samples, which were analyzed using

inductively coupled plasma atomic emission spectroscopy (ICP-AES).

An experimental study was performed to identify optimal SLM processing parameters for this

new Ti35Zr28Nb alloy, because these were not available. The optimization of processing

parameters was as follows: (i) a range of processing parameters were used to process the

samples, (ii) defects were evaluated for all the samples, and (iii) the optimum processing

parameters were identified as those for test number 8 in Table 2 for the samples with the

highest density and the highest build quality. The samples were processed with the following

processing parameters: varying laser power (P), scanning speed (v), energy density (Ed), at

constant hatch spacing (h = 0.12 mm) and layer thickness (t = 0.03 mm), as indicated in

Table 2. Defects such as voids, gaps and cracks of the SLM-manufactured samples were

examined using X-ray computed tomography (X-ray CT) (Phoenix v|tome|x, GE) with a 20

μm resolution. All dimensions have been studied using post-processing software including

Autodesk Meshmixer and myVGL (Volume Graphics) on the CT-scanned data. The

Archimedes method was used to measure the density and calculate the porosity of the SLM-
manufactured samples. The density measurements were repeated three times for each sample

to obtain reliable results and the average value is calculated. The optimum processing

parameters were identified as the processing parameters used in the fabrication of the samples

that exhibited the highest density (i.e. close to the theoretical density of the Ti35Zr28Nb alloy)

and the highest building quality (without defects or gaps). This study identified the

processing parameters for Test no. 8 (i.e., P = 140 W, v = 486 mm/s, and Ed = 80 J/mm3) as

the optimal processing parameters. These parameters were then used for the fabrication of the

Ti35Zr28Nb alloy bulk and scaffold samples for further microstructure characterization and

evaluation of their mechanical, corrosion, and biological properties.

SLM was used to fabricate porous Ti35Zr28Nb samples with two types of porous structures,

i.e., face centered cubic unit cells with longitudinal struts (FCCZ) and face and body centered

cubic unit cells with longitudinal struts (FBCCZ). The FCCZ and FBCCZ structures were

expected to have high strength and elastic modulus in the longitudinal direction [44, 45].

2.2 Macro- and micro-structural characterization

Phase identification of the SLM-manufactured Ti35Zr28Nb bulk samples was carried out

using X-ray diffraction (XRD) (PANalytical X’Pert Pro diffractometer, Netherlands) with Cu

Ka radiation at 40 kV and 40 mA. The macro-porous structures of the FCCZ and FBCCZ

samples were characterized using X-ray CT. The microstructures of the SLM-manufactured

Ti35Zr28Nb bulk samples were characterized using optical microscopy (OM), field emission

scanning electron microscopy (FEI-SEM) (Supra 55, Zeiss), and high-resolution transmission

electron microscopy (HRTEM) (JEOL-2010, Japan). The SEM samples were prepared by

grinding with silicon carbide (SiC) abrasive papers up to 4000 grit, polishing, and etching

with Kroll’s reagent. To prepare samples for TEM analysis, disc specimens (with a thickness

of 300 μm and a diameter of 3 mm) were produced using electrical discharge machining
(EDM). The thickness of the disc specimens was ground down to 80 μm using SiC abrasive

papers. Subsequently, the specimens were dimpled to 20 μm thickness using a dimple grinder

(Gatan Inc., Model 656), and further ion-sliced to around 100 nm thickness using an ion

slicer (JEOL, 09100IS).

2.3 Mechanical properties

The compressive properties of SLM-manufactured Ti35Zr28Nb bulk and porous samples

with dimensions of 8 mm x 8 mm x 12 mm were evaluated using compression tests, which

were carried out on a 30 kN Instron Universal Tester (Instron 5567, USA) equipped with a

non-contacting video extensometer. The samples were tested at a deformation rate of 0.001

mm/s. The strain was measured using a high-resolution digital camera. All measured data and

test parameters were recorded using Bluehill software. The elastic modulus and yield strength

for the bulk samples, and the elastic modulus and plateau strength for the porous samples

were calculated based on the resultant compressive stress–strain curves. The plateau strength

was calculated as the mean of the stresses between 20 % and 30 % compressive strain

according to ISO 13314 [46].

2.4 Corrosion properties

The corrosion properties of the SLM-manufactured Ti35Zr28Nb bulk samples were evaluated

using a VSP-300 Potentiostat (Bio-logic France) by the measurement of polarization curves

and electrochemical impedance spectroscopy (EIS). A three-electrode cell was used [47, 48].

The working electrode was the specimen mounted in epoxy resin with electrical connection

made with an insulated silver wire embedded in the epoxy. A saturated calomel electrode

(SCE) was the reference electrode, and a 1.5 cm × 1.5 cm platinum electrode was the counter

electrode. Polarization curves and electrochemical impedance spectra of the samples were

measured in Hanks’ solution at 37 ± 0.5 ℃. The Hanks’ solution had the following
composition (mg/L): 0.14 CaCl2, 0.40 KCl, 0.06 KH2PO4, 0.10 MgCl2·6H2O, 0.10

MgSO4·7H2O, 8.00 NaCl, 0.35 NaHCO3, 0.048 Na2HPO4, 1.00 glucose, and 0.01 phenol red

(mg/L). Prior to testing, the epoxy-mounted specimens were polished with 1200 grit SiC

paper, degreased with acetone and ethanol, rinsed with distilled water, and dried in a stream

of warm air. The polarization plots were obtained, after stabilization for 2 h immersion in

Hanks’ solution, in the range −1.0 to 2.6 V versus the corrosion potential at a scan rate of 5

mV/s. EIS was measured in the frequency range from 100 kHz to 10 MHz with a sinusoidal

potential amplitude of 10 mV [49-51].

2.5 In vitro biocompatibility

The in vitro biocompatibility of the SLM-manufactured Ti35Zr28Nb porous FCCZ and

FBCCZ samples were assessed using human osteoblast-like cells (SaOS2) (Barwon

Biomedical Research, Geelong Hospital, Australia) as SaOS2 cells are of human origin,

possess a number of osteoblast-like properties, and can be used as a model for studying

human osteoblasts [52-54]. The cells were cultured in minimum essential medium alpha

(MEM α, Gibco) supplemented with 10% fetal bovine serum (FBS, Gibco) and 1% penicillin

/ streptomycin in an incubator with a humidified atmosphere of 5% CO2 at 37 °C. The

medium was changed every three days. After confluence, the cells were detached from the

flask using 0.05% trypsin–EDTA (Gibco) and then sub-cultured.

Prior to in vitro assessment, the SLM-manufactured porous samples were washed using

ultrasonic cleaning in acetone, ethanol, and water, each step for 15 min. All samples then

were sterilized in 70% ethanol for 2 h on an orbital shaker, and air-dried in a biohazard hood

for 2 h [52]. The samples were placed into the wells of a 48-well plate. Each well contained a

specimen, was filled with 400 μl cell culture medium, and was seeded with 8000 cells. Wells

seeded with the same number of cells without the presence of the samples were used as the

control groups. After cell culture, each well was washed three times with phosphate-buffered
saline (PBS). The samples in a well were transferred into a new well of a 48-well plate.

Afterwards, each well was filled with 300 μl fresh red-free media.

The number of cells in each well was measured using the MTS assay. Each well was added

100 μl MTS/PMS solution, and the well plate was placed in an incubator for 1 h at 37 °C.

Afterwards, the well plate was removed from the incubator and 100 μl solution from each

well was transferred into a 96-well plate. The optical density (OD) of each well in the 96-well

plate was measured at the wavelength of 490 nm by a microplate reader (FlexStation 3

Microplate Reader, Waltham, CA, USA). The number of cells is linearly related to the OD.

Finally, the absorbance of each sample was divided by the absorbance of the control wells to

obtain cell viability values as a percentage of the control. The numbers of cells that adhered

to the SLM-manufactured Ti35Zr28Nb scaffolds and the control were also measured using

the MTS array and further divided by the section area of the sample to obtain the cell

adhesion density [11].

For the cell adhesion observations, SLM-manufactured porous samples were placed in a 48-

well plate. Each well was filled with 300 μl media with 1× 104 SaOS2 cells and incubated at

37 °C in 5% CO2 humidified air for 7 d, 14 d, and 28 d, respectively. Afterwards, the samples

in the wells were washed using PBS three times, and fixed in 3.9% glutaraldehyde solution

for 20 min at room temperature, rinsed three times with PBS, and finally dehydrated using an

ethanol/distilled water gradient (50%, 60%, 70%, 80%, 90%, and 100%, for 10 min each) and

a hexamethyldisilazane (HMDS) solution for 30 minutes. SaOS2 cells adhered to the surfaces

of the SLM-manufactured samples were observed by FEI-SEM (Verios 460L).

2.6 Statistical analysis

At least five repeats of the compression tests, three repeats of the corrosion tests, and in vitro

biocompatibility assessments for each group of samples were carried out. One-way variance
analysis (IBM SPSS Statistics) was applied to determine the statistical significance of the

differences between groups. P < 0.05 was considered statistically significant.

3. Results and discussion

3.1 Microstructure

Table 1 presents the composition of the Ti35Zr28Nb alloy powder and the SLM-

manufactured bulk samples. There were no significant changes in the concentrations of the

main alloying elements, Nb and Zr, caused by the SLM process. However, the oxygen

content increased from 0.09 wt.% in the metal powder to 0.16 wt.% after SLM. This is

consistent with a previous study [37]; the oxygen increase is attributed to the residual oxygen

content in the SLM work chamber, which could not be completely removed by evacuating

the SLM machine [55]. The SLM-manufactured Ti35Zr28Nb bulk sample exhibited a

porosity of 2.0 ± 0.2 % and a density of 5.80 ± 0.02 g/cm3 which was 98% of the theoretical

density of the alloy.

The microstructure in the longitudinal and transverse sections of the SLM-manufactured

Ti35Zr28Nb samples were characterized using XRD, SEM, and TEM. The longitudinal

direction is the build-up direction during SLM and the transverse direction is orthogonal to

the longitudinal direction. The longitudinal section is the surface that is normal to the

longitudinal direction and the transverse section is the surface that is normal to the transverse

direction. Fig. 2 presents the XRD patterns of the metal powder and the SLM-manufactured

bulk samples in both longitudinal and transverse directions. The three samples showed the

same β phase crystal structure, similar to that of the as-cast Ti35Zr28Nb alloy [16, 56]. Fig. 3

shows the HRTEM images of the SLM-manufactured samples. The bright-field image

obtained from the longitudinal section and the dark-field image of the phases of interest in the

longitudinal section overlain in color (source reflections circled) are shown in Figs. 3(a) and
(b). The inserts show the selected area electron diffraction (SAED) patterns coinciding with

the imaged regions, Figs. 3(c) and (d). The SAED patterns along with the bright-field and

dark-field imaging of the reflections were obtained from the areas of interest. These results

confirm that the SLM-manufactured Ti35Zr28Nb bulk sample in both longitudinal and

transverse directions was composed of a β phase, consistent with the XRD results (Fig. 2).

Fig. 4 shows the surface morphologies of the SLM-manufactured Ti35Zr28Nb bulk samples

in both longitudinal and transverse sections. Figs. 4(a) and (b) show the subgrain-features

inside the primary grains in the samples in both longitudinal and transverse sections. Fig. 4(a)

shows the tracks of the melt pool due to the individual melted layers that developed at each

crossing of the laser in the longitudinal section, revealing the characteristic microstructure of

SLM-processed samples. Similarly, Fig. 4(b) shows the typical pattern of laser tracks in the

transverse section. Sing et al. [57] reported similar microstructures in a SLM-processed Ti

alloy containing 50 wt.% Ta. The etched surface of the SLM-manufactured samples showed a

cellular structure due to the shallowly etched cell boundaries and the more deeply etched cell

interiors (Fig. 4(c)). The diameter of the cells varied in different regions and exhibited an

average value of around 400 nm (Fig. 4(d)). The cells were mostly spherical or elliptical,

whereas there were also some tubular cells. The cells were columnar in shape. Olsen et al.

[58] reported a similar subgrain cellular structure in an SLM-manufactured stainless steel

(316L).

The CAD models of the FCCZ and FBCCZ structures are shown in Figs. 5(a) and (b),

respectively. The dimensions of the unit cells for both porous structures for the SLM-

manufactured samples were 2 mm x 2 mm x 2 mm with a strut diameter of 0.3 mm. Figs. 5(c)

and (d) show the SEM images of the FCCZ and FBCCZ scaffolds fabricated by SLM, and

Figs. 5(e)–(f) show the surface morphologies of the FCCZ and FBCCZ scaffolds,
respectively. Partially melted metal particles of the alloy were deposited on the surfaces of

the samples (Figs. 5(c)–(f)).

The Archimedes method was used to measure the density of the SLM-manufactured bulk and

scaffold samples, from which the porosity was calculated. The porosity values of the two

porous models were 87.3% for the FCCZ and 78.9% for the FBCCZ, respectively, while the

porosity values of the two SLM-manufactured porous scaffolds were 83.2 ± 2.3 % for the

FCCZ and 49.9 ± 3.2 % for the FBCCZ, respectively. The porosity of the FCCZ sample was

close to the expected theoretical porosity, but the SLM-manufactured FBCCZ sample showed

a porosity significantly lower than the theoretical porosity. This is because there were more

partially melted metal particles deposited on the surfaces of the struts inside the FBCCZ

porous structure than in the FCCZ structure.

3.2 Mechanical properties

Fig. 6 shows the compression properties of the SLM-manufactured Ti35Zr28Nb bulk and

porous samples in both longitudinal and transverse directions. The compression stress–strain

curves of the bulk samples in both longitudinal and transverse directions show typical plastic

deformation behavior: (i) an elastic stage; (ii) a plastic yield plateau stage (the stress increases

linearly with the strain); and (iii) a parabola stage (Fig. 7(a)), indicating considerable plastic

deformation of the SLM-manufactured samples. The Ti35Zr28Nb alloy manufactured by the

conventional ingot method showed similar deformation behavior [16]. Yang et al. [59] also

reported similar plastic deformation behavior in a Ti22.4Nb0.73Ta2Zr1.34O alloy

manufactured by the ingot method.

The compression stress–strain curves of the SLM-manufactured porous structures with FCCZ

and FBCCZ structures in both longitudinal and transverse directions show the universal

deformation behavior of metal foams [18], i.e. an initial elastic deformation region, a long
plateau region (at a nearly constant flow stress to a large strain), and a densification region

(the flow stress rapidly increases) (Fig. 7(b)). The mechanical properties of the SLM-

manufactured Ti35Zr28Nb bulk and porous samples are summarized in Figs. 6(c) and (d),

respectively, and listed in Table 3. Table 3 indicates that the elastic modulus values of the

SLM-manufactured bulk samples in the longitudinal and transverse directions were 57.0 ±

1.8 % GPa and 60.2 ± 2.0 % GPa, respectively, which did not show any significant difference.

The compressive yield strengths of the bulk samples in the longitudinal and transverse

directions were 612 ± 29 MPa and 768 ± 30 MPa, respectively. The compressive yield stress

in the longitudinal direction was lower than that in the transverse direction for the SLM-

manufactured bulk samples. This was probably due to the different microstructures in the

different directions processed by SLM (Figs. 4(a) and (b)).

Table 3 shows that the mechanical properties of the SLM-manufactured Ti35Zr28Nb porous

samples were affected by both the porous structure and the porosity of the scaffolds. The

elastic modulus and plateau strength values of the SLM-manufactured FCCZ structures were

1.1 ± 0.1 GPa and 0.7 ± 0.1 % GPa, and 27 ± 2 MPa and 8 ± 2 MPa, in the longitudinal and

transverse directions respectively, indicating higher elastic modulus and plateau strength in

the longitudinal direction than in the transverse direction. The elastic modulus and plateau

strength values of the SLM-manufactured FBCCZ structures were 1.3 ± 0.1 GPa and 1.0 ±

0.1 GPa, and 58 ± 3 MPa and 45 ± 2 MPa, in the longitudinal and transverse directions

respectively, like the FCCZ structures indicating higher elastic modulus and plateau strength

in the longitudinal direction than in the transverse direction. The higher elastic modulus and

plateau strength in the longitudinal direction than in the transverse direction are as expected,

because there were additional longitudinal struts in the designed FCCZ and FBCCZ

structures, which provided stronger support in the longitudinal direction (Fig. 5).
The SLM-manufactured FBCCZ structures showed higher elastic modulus and plateau

strength values than the FCCZ structure (Table 3). This was mainly caused by the porosity of

the FCCZ structure (83.2 ± 2.3 %) higher than the FBCCZ structure (49.9 ± 3.2 %). The

Gibson and Ashby model [18, 60] indicates that the relative density, ρ/ρb (the ratio of the

density of the porous metal ρ to that of the bulk ρb) is the most important structural

characteristic of a porous metal that influences its mechanical response. The relationships

between the plateau strength (σps), the elastic modulus (E), and the relative density can be

approximated by [60]:

E = a1(ρ/ρb)m1Eb (1)

σps = a2(ρ/ρb)m2σys (2)

where σys and Eb are the yield strength and the elastic modulus of the bulk material,

respectively. The constants a1, a2, m1, and m2 are related to the pore geometry and the

material of the struts, and are in the ranges of 0.1–4 and 0.1–1, respectively [60]. It is

recommended that the constants a1, a2, m1, and m2 should be 1, 0.3, 2, and 1.5 for a wide

range of open-cell metal foams, respectively [18, 60]. Ataee et al. [35, 37] and Yan et al. [61]

also reported that the mechanical properties of metal scaffolds fabricated by EBM and SLM

were affected by both the pore geometry and the porosity of the scaffolds. The SLM-

fabricated gyroid CP-Ti scaffolds mostly composed of harder martensite α phase and

exhibited elastic modulus and plateau strength in the range of 1.5-2.7 GPa and 59-75 MPa

with excellent ductility up to 50% [37]. Wauthle et al. [62] also reported that the mechanical

properties of SLM-fabricated dodecahedron structured CP-Ti scaffolds with the porosity

range of 66-82% exhibited the elastic modulus and plateaue strength in the range of 0.6-2.6

GPa and 14-63 MPa, respectvely. Similarly, SLM-fabricated triply periodic minimal surface

(TPMS) structures of Ti64 (α+β) with a porisity range of 80-95% exhibited elastic modulus

in the range of 0.12-1.25 GPa [61]. The SLM-manufactured β-Ti35Zr28Nb scaffolds with
FCCZ and FBCCZ structures showed elastic modulus values ranging from 0.7 to 1.3 GPa and

plateau strength values ranging from 8 to 58 MPa, both falling within the mechanical

property range of trabecular bone. The mechanical properties of SLM-manufactured

Ti35Zr28Nb scaffolds with FBCCZ and FBCCZ structures showed the same trend as SLM-

manufactured Ti64 with the same porous structures [45].

3.3 Corrosion behavior

The corrosion behavior of the SLM-manufactured Ti35Zr28Nb bulk samples in Hanks’

solution was investigated using an electrochemical analysis through polarization and

electrochemical impedance spectroscopy (EIS) while as-cast CP-Ti was included as a

reference. All tests were carried out on the surfaces of the as-cast CP-Ti and the longitudinal

and transverse sections of the SLM-manufactured bulk samples with the same surface

preparation. Fig. 7(a) shows the current-time plots of the SLM-manufactured bulk samples

and the CP-Ti after immersion in Hanks’ solution for 2 h at 37 ± 0.5 °C. In the initial range

from 0 to 290 s, the current density of the SLM-manufactured samples was higher than that

of the CP-Ti. However, the current density of the CP-Ti increased and reached ~5.2 x 10-4

mA/cm2 at ~290 s, showing the same value as that of the SLM-manufactured samples. In the

range of 290–415 s, the current density of the CP-Ti exhibited a much higher value than that

of the SLM-manufactured samples, indicating stronger polarization of the SLM-

manufactured samples.

Fig. 7(b) shows the polarization plots of the SLM-manufactured Ti35Zr28Nb bulk samples in

the longitudinal and transverse sections and the CP-Ti after immersion in Hanks’ solution at

37 ℃ for 2 h. The results of polarization curves for SLM-manufactured Ti35Zr28Nb bulk

samples immersed in Hanks’ solution at 37 ± 0.5 ℃ (Figs. 7(a) and (b)) are summarized in

Table 4. The SLM-manufactured bulk samples and the CP-Ti displayed similar spontaneous
passive behavior, which indicates the spontaneous formation of passive films on the surfaces

of all samples [63]. The open-circuit potential (OCP) derived from the polarization plots (Fig.

7(b)) were −1.0627 V, −1.0006 V, and −0.6699 V for the SLM-manufactured bulk

longitudinal section, the SLM-manufactured bulk transverse section, and the CP-Ti,

respectively. The OCP is the potential of the working electrode relative to the reference

electrode when no potential or current is being applied to the corrosion system. The OCP of

CP-Ti was higher than that of the SLM-manufactured Ti alloys (Fig. 7(b)), which might be

caused by their different microstructures (Figs. 3 and 4) [63]. The Zr and Nb in the SLM-

manufactured Ti35Zr28Nb alloy can form Nb-O and Zr-O oxides on the surface after

immersion in Hanks’ solution in long-term, leading to easier passivation at a lower potential

and significantly enhanced anodic polarization that can decrease the current density (Table 4)

[63].

The current (I) of the CP-Ti increased somewhat with increasing applied potential in the

range from OCP to −0.05 VSCE (Fig. 7(b)), indicating a somewhat higher passive corrosion

rate compared with the SLM-manufactured samples. The current density of the SLM-

manufactured samples remained stable for corrosion potential up to 0.065 VSCE, indicating a

typical passivation region and the formation of passive films on the surfaces of the samples.

This passive film is important for ensuring low corrosion rates. For potentials over 0.65 VSCE,

there was a somewhat higher current density for the SLM-manufactured samples, which

might have been caused by transpassive.

A previous study reported that an as-cast Ti35Zr28Nb alloy was not sensitive to crevice

corrosion and exhibited low corrosion rates in Hanks’ solution at 37 °C and 3.5 wt% NaCl

solution at 95 °C [47]. The corrosion behavior of SLM-manufactured Ti35Zr28Nb alloy

scaffolds with FCCZ and FBCCZ structures in both solutions has also been reported [48].

The results indicate that SLM-manufactured Ti35Zr28Nb scaffolds with FCCZ and FBCCZ
structures exhibited no crevice corrosion, had low corrosion rates, and were spontaneously

passive in both solutions.

To further verify the electrochemical properties of the SLM-manufactured Ti35Zr28Nb bulk

samples and the CP-Ti, EIS tests were performed at the OCP in Hanks’ solution at 37 °C. The

corrosion behavior, including Nyquist plots, Bode frequency plots, and Bode phase plots of

the SLM-manufactured samples and the CP-Ti, are shown in Figs. 7(c)–(f). Fig. 7(c)

indicates that the modulus of impedance (Z) of the SLM-manufactured samples was

significantly larger than that of the CP-Ti, indicating better electrochemical behavior. In the

case of the Bode plots vs. frequency (Figs. 7(e) and (f)), although all samples showed an

increase in impedance from high frequency to low frequency, the CP-Ti exhibited the lowest

impedance values across the whole range.

Figs. 7(c) and (d) indicate that the SLM manufactured Ti-Zr-Nb alloys and CP-Ti in Hanks’

solution show a similar corrosion behavior, which is caused by the spontaneous passive film

formation on the surfaces [63]. Bai el at. [63] reported that stable Nb2O5 and ZrO2 layers

could be formed underneath of the outer layer of porous TiO2 on the surface of a Ti-alloy

containing Zr and Nb, while an outer porous TiO2 layer and an inner dense TiO2 layer formed

on CP-Ti. Fig. 7(f) shows two capacitive behaviors for the SLM-manufactured Ti alloys and

CP-Ti, which is in good agreement with the results reported in [62]. To characterize the

passive layers on the surfaces of the samples, an equivalent circuit (Fig. 7(c)) was used to fit

the EIS plots. The equivalent circuit consisted of two circuits in series with R1-CPE1 to R2-

CPE2 in parallel combination, and the two were in series with Rs (which represents the

solution resistance). The fitting results are summarized in Table 5. In this model, the passive

layer presents a duplex structure: a porous outer layer and an inner barrier layer. For the two

circuits in parallel combination, R1 and R2 represent the resistances of the outer porous layer

and the inner barrier layer, respectively, and are associated with the charge transfer resistance
through the porous layer. The constant phase elements (CPE1 and CPE2) have a capacitance

(C1 and C2) and an associated phase angle (n1 and n2) and are in parallel with the resistive

elements (R1 and R2).

Table 5 indicates that the CP-Ti exhibited higher capacitance (C1 and C2) and lower

resistance in both layers (R1 and R2) than those of the SLM-manufactured samples. In general,

low capacitance and high resistance indicate the high stability of a passive layer on a sample

in Hanks’ solution. The SLM-manufactured Ti35Zr28Nb bulk samples possessed passive

behavior and good electrochemical corrosion behavior, both of which are consistent with the

results of the polarization tests. In addition, the resistance (R2) of the inner barrier layer was

greater by a factor of around 17 – 62 times compared with the outer porous layer (R1) –

which indicates that the inner barrier layer was more important than the outer porous layer in

relation to protection from corrosion. In addition, the capacitance of the inner barrier layer

(C2) was much lower than that of the outer porous layer (C1), which further demonstrates the

stability of the inner barrier layer on the surfaces of the SLM-manufactured samples.

3.4 In vitro biocompatibility

Fig. 8 shows the cell viability and adhesion of the SaOS2 cells on the SLM-manufactured

Ti35Zr28Nb scaffolds with FCCZ and FBCCZ structures as compared to the control. The cell

viability of the FCCZ and FBCCZ samples was not significantly different from that of the

control, indicating the excellent biocompatibility of the SLM-manufactured scaffolds (Fig.

8(a)). The morphologies of the cell adhesion on to the surfaces of the SLM-manufactured

scaffolds after cell culturing for 7 d, 14 d, and 28 d are shown in Figs. 8(b), (c), and (d),

respectively. The SaOS2 cells adhered to the surfaces of the scaffolds and exhibited a

polygonal and full spreading shape with filopodia, lamellipodia, and peripheral ruffles after

culturing for 7 d (Fig. 8(b)), indicating that the cells were compatible with the surfaces and
grew in a healthy way. With increasing cell culture time to 14 d and 28 d, the cells spread

across the surfaces of the scaffolds and covered all of the surface area, as shown in Figs. 8(c)

and (d), respectively. Overall, the SaO2 cells on the surfaces of the SLM-manufactured

scaffolds exhibited healthy morphology, attachment, and spreading, as indicated by the

flourishing growths of filopodia with widely extended microspikes solidly attached to the

surfaces of the scaffolds, highly magnified in Fig. 8(d).

The cell adhesion density in relation to both the Ti35Zr28Nb FCCZ and FBCCZ scaffolds

was lower than that of the control, and the cell adhesion density in relation to the FCCZ

scaffold was lower than that of the FBCCZ scaffold (Fig. 8(a)). The surface area of cell

adhesion of the FCCZ scaffold was lower than that of the FBCCZ scaffold because the

porosity was ~83.2% for the FCCZ and ~49.9% for the FBCCZ. A low surface area of cell

adhesion will lead to smaller numbers of cells adhering to the surface. Figs. 5(e) and (f) show

that the surfaces of the SLM-manufactured scaffolds were mostly coved by partially melted

alloy particles, which not only decreases the pore space but also increases the surface

roughness, as the average particle diameter is ~45 µm. SaSO2 cells were reported to favor

surfaces with roughness within a few micrometers [11, 64, 65]. The surface roughness of the

SLM-manufactured scaffolds was much greater than a few micrometers, which would have

significantly affected the cells’ seeding on these surfaces, making it more difficult for the

cells to settle on the surfaces (Figs. 8(b), (c), and (d)). This is why the cell adhesion density of

the FCCZ and FBCCZ structures was lower than that of the control. This raises a challenge

for the SLM process: the surface roughness of an SLM-manufactured product should be

effectively reduced, and any partially melted metal particles deposited on the surfaces of the

resultant scaffolds should be removed as far as possible.

4. Conclusions
Selective laser melting (SLM) was used to successfully fabricate new β-Ti35Zr28Nb alloy

scaffolds for biomedical applications. The SLM-manufactured bulk samples showed elastic

modulus values of 57 and 60 GPa, and compressive yield strength values of 612 and 768

MPa in the longitudinal and transverse directions, respectively. The SLM-manufactured

scaffold (FCCZ) with a porosity of 83% exhibited elastic modulus values of 1.1 and 0.7 GPa,

and compressive yield strength values of 27 and 8 MPa in the longitudinal and transverse

directions, respectively. The SLM-manufactured scaffold (FBCCZ) with a porosity of ~50%

exhibited elastic modulus values of 1.3 and 1.0 GPa, and compressive yield strength values of

58 and 45 MPa in the longitudinal and transverse directions, respectively. The porosity of the

FBCCZ scaffolds was significantly lower than that of the designed porosity attributed to

more partially melted metal particles deposited on the surfaces of the struts inside the porous

structure. The SLM-manufactured Ti35Zr28Nb scaffolds exhibited good corrosion behavior

and biocompatibility.

Acknowledgements

The authors acknowledge the financial support for this research by the National Health and

Medical Research Council (NHMRC), Australia, through grant GNT1087290; and the

Australian Research Council (ARC) through the discovery grant DP170102557. YL is also

supported through an ARC Future Fellowship (FT160100252). The authors also acknowledge

the scientific and technical assistance of RMIT’s Advanced Manufacturing Precinct (AMP)

and RMMF (RMIT University’s Microscopy and Microanalysis Facility, a linked laboratory

of the Australian Microscopy & Microanalysis Research Facility). The technical assistance of

Mr. Aaron Pateras of AMP is gratefully acknowledged.

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Statement of Significance

Novel β Ti35Zr28Nb alloy scaffolds with FCCZ and FBCCZ structures were successfully

fabricated by selective laser melting (SLM) for biomedical applications. The scaffolds

showed values of elastic modulus of ~1 GPa and plateau strength of 8-58 MPa, which fall

within the ranges of the mechanical properties of trabecular bone. The SLM-manufactured β

Ti35Zr28Nb alloy showed good corrosion properties. Both SLM-manufactured FCCZ and

FBCCZ scaffolds exhibited good biocompatibility, with osteoblast-like cells attaching,

growing, and spreading in a healthy way on their surfaces after culturing for different periods

up to 28 d.
Table 1 Compositions of Ti35Zr28Nb alloy powder and SLM-manufactured alloy samples*

Sample Chemical composition (wt%)

Ti N C O H Fe Al V Ni Nb Zr
Powder Bal <0.005 <0.01 0.09 <0.002 0.02 0.03 <0.01 0.01 27.7 35.4
SLM Bal 0.009 0.03 0.16 0.002 0.04 0.08 0.02 0.02 28.5 34.1
*
compositions of Sn, Ru, Pd, Co, Mo, Cr: less than 0.01%.

Table 2 Testing parameters used in fabricating Ti35Zr28Nb alloy samples using SLM*

Test No. 1 2 3 4 5 6 7 8 9 10 11 12 13
P (w) 100 100 100 100 140 140 140 140 180 180 180 180 100
v (mm/s) 694 462 396 347 972 648 555 486 1250 833 714 694 385
Ed
40 60 70 80 40 60 70 80 40 60 70 72 72
(J/mm3)
*
for all the samples: hatch spacing h = 0.12 mm, and layer thickness t = 0.03 mm.

Table 3 Mechanical properties of SLM-manufactured Ti35Zr28Nb bulk and porous samples

Porosity Elastic Modulus Yield Strength

Sample Plateau Strength (MPa)
(%) (GPa) (MPa)
57.0 ± 1.8* 612 ± 29* -
Bulk 2.0 ± 0.2
60.2 ± 2.0** 768 ± 30** -
1.1 ± 0.1* - 27 ± 2*
FCCZ 83.2 ± 2.3
0.7 ± 0.1** - 8 ± 2**
1.3 ± 0.1* - 58 ± 3*
FBCCZ 49.9 ± 3.2
1.0 ± 0.1** - 45 ± 2**
*
longitudinal direction; **transverse direction.

Table 4 Results of polarization curves for SLM-manufactured Ti35Zr28Nb bulk samples

immersed in Hanks’ solution at 37 ± 0.5 ℃

OCP Eb Ipass Passive range

Material
(VSCE) (VSCE) (mA cm−2) (VSCE)
Transverse -1.0627 0.1183 0.0314 ± 0.0016 1.1810
Longitudinal -1.0006 0.0638 0.0383 ± 0.0019 1.0644
CP-Ti -0.6699 / 0.1464 ± 0.0126 /

Table 5 Fitting results of EIS spectra for SLM-manufactured Ti35Zr28Nb bulk samples

Specimen Rs (Ω cm2) R1 (kΩ cm2) C1 (10-6 F cm-2) n1 C2 (10-6 F cm-2) n2 R2 (MΩ cm2)
Transverse 42.54 ± 0.04 199.62 ± 0.48 18.82 ± 0.24 0.8356 5.34 ± 0.11 0.9882 12.56 ± 0.15
Longitudinal 30.82 ± 0.06 145.11 ± 0.59 28.89 ± 0.13 0.8372 9.5 ± 0.21 0.9978 6.01 ± 0.09
CP-Ti 30.05 ± 0.07 46.47 ± 0.26 38.32 ± 0.31 0.7716 12.21 ± 0.35 0.9559 0.81 ± 0.14