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Research paper
L.E. Murr a,b,∗ , K.N. Amato a,b , S.J. Li c , Y.X. Tian c , X.Y. Cheng c , S.M. Gaytan a,b ,
E. Martinez a,b , P.W. Shindo a,b , F. Medina b , R.B. Wicker b,d
a Department of Metallurgical and Materials Engineering, The University of Texas at El Paso, El Paso, TX 79968, USA
b W. M. Keck Center for 3D Innovation, The University of Texas at El Paso, El Paso, TX 79968, USA
c Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China
d Department of Mechanical Engineering, The University of Texas at El Paso, El Paso, TX 79968, USA
A R T I C L E I N F O A B S T R A C T
Article history: Total knee replacement implants consisting of a Co–29Cr–6Mo alloy femoral component
Received 11 February 2011 and a Ti–6Al–4V tibial component are the basis for the additive manufacturing of novel
Received in revised form solid, mesh, and foam monoliths using electron beam melting (EBM). Ti–6Al–4V solid
14 April 2011 prototype microstructures were primarily α-phase acicular platelets while the mesh
Accepted 6 May 2011 and foam structures were characterized by α′ -martensite with some residual α. The
Published online 12 May 2011 Co–29Cr–6Mo containing 0.22% C formed columnar (directional) Cr23 C6 carbides spaced
∼2 µm in the build direction, while HIP-annealed Co–Cr alloy exhibited an intrinsic stacking
fault microstructure. A log–log plot of relative stiffness versus relative density for Ti–6Al–4V
and Co–29Cr–6Mo open-cellular mesh and foams resulted in a fitted line with a nearly ideal
slope, n = 2.1. A stress shielding design graph constructed from these data permitted mesh
and foam implant prototypes to be fabricated for compatible bone stiffness.
c 2011 Elsevier Ltd. All rights reserved.
⃝
∗ Corresponding author at: Department of Metallurgical and Materials Engineering, The University of Texas at El Paso, El Paso, TX 79968,
USA. Tel.: +1 915 747 6929; fax: +1 915 747 8036.
E-mail address: lemurr@utep.edu (L.E. Murr).
c 2011 Elsevier Ltd. All rights reserved.
1751-6161/$ - see front matter ⃝
doi:10.1016/j.jmbbm.2011.05.010
J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S 4 (2011) 1396–1411 1397
corrosion resistance (Niinomi, 2001, 2008). However, the vast structures from any available pre-alloyed powder by additive
majority of these implant applications utilize monolithic (layer-based) manufacturing directly from computer (CAD)-
(solid) Ti alloy appliances which have exhibited limited generated models using directed laser or electron beams have
lifetimes as a consequence of incomplete or lacking fusion been demonstrated. Harryson and Cormier (2005) described
or bone cell ingrowth, and elastic modulus mismatch. Other the fabrication of custom (or patient-specific) orthopedic
issues, relating to implant efficiency include the absence implants using electron beam melting (EBM). Hollander et al.
of vascularization, and in situations such as knee implant (2006), Multen et al. (2009) and Stamp et al. (2009) utilized
appliances in particular, the production of wear debris at selective laser melting (SLM) to produce regular or periodic
bearing surfaces. (reticulated) mesh structures and stochastic foam structures
Elastic modulus mismatch, or stress shielding, is a major while Heinl et al. (2007, 2008) produced Ti-alloy mesh arrays
feature of metallic implant—bone incompatibility. Since bone corresponding to porosities or densities having stiffnesses
tissue remodels itself in response to applied stress, stress (elastic constants) approaching bone stiffnesses (in excess of
reduction leads to bone loss or resorption. Consequently, 20 GPa). Cellular Ti–6Al–4V fabricated by EBM for orthopaedic
high modulus (or stiff) implant material dominates the load implants has also been described by Marin et al. (2010).
bearing regime in contrast to low modulus bone. Cortical or More recently, Murr et al. (2010) illustrated a wide range of
hard bone can have elastic moduli ranging from 3 to 30 GPa, Ti–6Al–4V reticulated mesh and stochastic foam prototypes
while the softer (intramedulary) trabecular or cancellous fabricated by EBM, and demonstrated that these open-cellular
bone has significantly lower elastic moduli: 0.02–2 GPa (Yang structures behaved similarly to a wide range of metallic
et al., 2001). This is in contrast to ∼110 GPa for variously foams, especially aluminum and aluminum alloys which
processed Ti–6Al–4V which has dominated the manufacture follow the Gibson and Ashby (1997) relationship:
of commercial implants over the past decade (Long and
E = α1 Es (ρ/ρs )n (1)
Rack, 1998; Chuna et al., 2003; Niinomi, 2007). Many knee
replacements also utilize Co–Cr–Mo alloys especially for where E is the elastic (Young’s) modulus (or stiffness at
superior wear resistance, but these alloys have even higher a corresponding density, ρ), and Es and ρs are the solid
moduli: ∼210 GPa. (full density) stiffness and full density, respectively. While
An effective strategy for reducing or eliminating stress generally n is approximated by 2, the experimental value
shielding and simultaneously enhancing osteoconductivity has been shown to vary from ∼1.8 to 2.2. Murr et al. (2010)
and bone cell ingrowth, has been the development of porous demonstrated that for Ti–6Al–4V mesh and foam prototypes,
metallic structures such as foams, which can be tailored to n = 2.3. In addition, it was demonstrated that complex, 3D
more closely match the modulus or stiffness of bone, thereby implant monoliths incorporating functionally-graded mesh
minimizing or eliminating stress shielding. Open cellular or foam or mesh/foam density variations and solid sections
foams and other porous structures are required for bone could be fabricated by EBM.
cell ingrowth to be effective in optimizing biocompatibility. In the present study, we focus on the fabrication of open
While there has been considerable effort in developing Ti cellular mesh and foam components of a Co–Cr–Mo alloy
and Ti-alloy foams (Dunand, 2004; Ryan et al., 2006; Singh (ASTM F-75) and Ti–6Al–4V using EBM for a range of densities
et al., 2010) the development of practical, biomedical implants and measured stiffnesses. In addition, these structures are in-
incorporating porosity in surface coatings has been minimally corporated into Co–Cr femoral and Ti–6Al–4V tibial prototypes
successful, and many commercial implants utilize some representing total knee replacement implants. The varying
form of surface porosity created by sintering sponge or density open cellular structures and their microstructures are
bead configurations or attaching other porous coatings to characterized by optical and scanning electron microscopy
the monolithic implant surface (Hacking et al., 2002; Bobyn and X-ray diffraction, while the corresponding microinden-
et al., 2005). The mechanical behavior of porous structures dation hardness for mesh strut structures and foam ligament
depends on pore volume fraction and size distribution. structures are measured along with dynamic Young’s modu-
In turn, these determine the strut size or ligament wall lus (dynamic stiffness number).
thickness and dimension partitioning the pores, and bearing
the load. In addition, pore size is also important for effective
bone ingrowth. The general consensus has been that a 2. Experimental procedures
minimum pore architecture or interconnectivity is in the
range of 100 µm (Holy et al., 2000; Freyman et al., 2001). 2.1. Fabrication of biomedical implant prototypes: The
Correspondingly, Yang et al. (2001) and Ryan et al. (2006) have EBM system
suggested larger pore sizes in the range of 500 µm–1 mm
promote the formation of fibrous tissues to optimize the Fig. 1 shows a schematic view of the Arcam A2 electron beam
biocompatibility. However, in contrast to solid, monolithic melting (EBM) system along with examples of the Ti–6Al–4V
implants fixed with acrylic cement, porous or porous-coated and Co-base (29% Cr, 6% Mo, 0.22% C, 0.25% Ni, 0.7% Si, 0.5%
implants must be initially stabilized with a precise press-fit to Mn, balance Co; in weight%) pre-alloyed powders used to
assure optimal bone tissue ingrowth. fabricate solid (fully dense) and more complex open cellular
While it is very difficult to custom fabricate monolithic structures as well as multifunctional monolithic biomedical
and complex Ti-alloy implants having designed porosity components. As illustrated in Fig. 1, an electron beam is
or stiffness features, new approaches utilizing solid free- generated in the electron gun at (1), and focused (2) and
form fabrication or rapid prototyping to build complex electromagnetically scanned (3) onto powder layers gravity
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fed from cassettes (4) and mechanically raked (5) into layers
roughly 75–100 µm thick. The powder layer thickness is
smaller for the smaller average powder size, which in the case
of the Ti–6Al–4V powder is ∼30 µm in contrast to the Co-base
alloy powder with an average diameter of ∼40 µm (Fig. 1). The
beam is selectively scanned by computer aided design (CAD)
software to melt specific layer portions which are added to
the next layer, ultimately forming a 3D (multilayer) structure
as the building component is lowered with each added layer
(6 in Fig. 1). Prior to the melt scan, the beam is rastered over
the newly raked layer in multiple (∼11) passes to preheat
the layer. The preheat scan rate is ∼104 mm/s with a beam
current of ∼30 mA, in contrast to the melt scan rate of
∼400 mm/s at a reduced beam current of 6–10 mA. Preheat
temperatures averaged ∼ 640 ◦ C–840 ◦ C for the Ti-alloy and
Co-base alloy, respectively. This is in contrast to melting
temperatures of 1625 ◦ C and 1430 ◦ C for the Ti-alloy and
the Co-base alloy, respectively. The building of 3D structures
by EBM from limited melt pools in the additive layers is a
form of directional solidification, with the solidification rate
determined in part by the beam scan and focus parameters
as well as the building structure geometries and dimensions,
and associated heat conduction and cooling rate. Thijs
et al. (2010) have recently discussed microstructural-build
related features, even epitaxial or columnar-grain orientation
variations in selective laser melting (SLM) fabrication of
Ti–6Al–4V in the context of scanning strategies, which include
beam scan direction or direction sequence, beam current,
scan speed, beam focus, etc. as discussed above.
2.2. Mesh and foam building software and modeling Fig. 1 – EBM system schematic (Arcam A2). Components
strategies are discussed in the text. Upper left SEM view shows
Ti–6Al–4V powder while lower left SEM view shows
Reticulated mesh structures and stochastic foams for Co–29Cr–6Mo powder.
Ti–6Al–4V and Co–29Cr–6Mo alloys were fabricated from
CAD software models developed from Materialise/Magics
(http://www.materialise.com) software and CT-scan models, foam samples (utilizing the CAD models demonstrated in
respectively as discussed in detail elsewhere (Murr et al., Fig. 2), using a resonant frequency analyser (IMCE-HTVP-
2010). The mesh array structure generator utilized a single 1750-C) for rectangular test specimens. The elastic modulus,
unit cell or lattice-structure unit referred to as a dode thin E, referenced to as the dynamic stiffness or stiffness-
element which varies in geometrical structure from 2-fold related number is proportional to the resonant frequency
to 3-fold symmetry axes with a rotation of 45◦ around the squared. These rectangular samples were supported by
longitudinal, reference axis (Fig. 2(a)). This build element small beams impacted lightly by a small hammer creating
feature and corresponding 3D model are illustrated in Fig. 2(a) a measurable resonant frequency. The test samples were
and (b), respectively. By varying the element dimensions nominally 2.3 cm × 2.3 cm × 3.6 cm in dimension or carefully
(Fig. 2(a)) the model size can be changed, including the machined to this dimension, which complied with the
strut diameters, and this produces density or corresponding general requirements discussed for metal foams by Ashby
porosity variations in the EBM fabricated components.
et al. (2000).
Utilizing CT scans for standard aluminum stochastic
open cellular foams, bitmap files representing image or
model slices with specific pixel dimensions were created 2.4. Mechanical testing for solid, full-density components
as illustrated in Fig. 2(c) and (d). These file representations and mesh and foam samples
(Fig. 2(c) and (d)) can be altered in linear dimension to create
variations in cell sizes and cell ligament dimensions resulting Mechanical behavior for solid and open-cellular structures for
in density and porosity variations (Murr et al., 2010). the Ti–6Al–4V and Co–29Cr–6Mo alloys fabricated by EBM was
investigated using Vickers microindentation hardness (HV)
2.3. Dynamic stiffness measurements for mesh and foam (Shimadzu HMV-2000 tester using a 100 gf load) and Rockwell
samples C-scale hardness (HRC) (using a 150 kgf load). HV and HRC
measurements were made for the solid EBM components
The elastic moduli (E) or Young’s moduli were measured for while HV measurements only using the 25 gf load were made
EBM fabricated Ti–6Al–4V and Co–29Cr–6Mo alloy mesh and for mounted and polished mesh struts and foam ligaments.
J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S 4 (2011) 1396–1411 1399
Fig. 2 – Reticulated mesh (a) and stochastic foam (b) models for EBM building of open cellular structures. In (a), the
dode-thin (Materialise/Magics) build element is shown on the left in cube and diamond orientations (0 and 45◦ ) which
correspond to the viewing arrows in the 3D model on the right. In (b), the foam pore and ligament structure is shown on the
left with a 3D model on the right.
A total of 25 Vickers indentations were made on each of two 2.5. Characterization of materials and microstructures
mounted sections from each sample were made to produce
100 HV values. Twenty-five HRC indentation values were Microstructures for the solid and open-cellular EBM fabri-
made for the solid sample. cated components were initially observed by optical metallog-
Tensile specimens were machined from solid Ti–6Al–4V raphy (OM), followed by scanning electron microscopy (SEM)
and transmission electron microscopy (TEM). The OM was
and Co–29Cr–6Mo specimens and tested in an upgraded
performed on sectioned, mounted, polished, and etched sam-
Tinius-Olson Universal Testing Machine (SIN 175118). The
ples using a digital imaging Reichert MEF4 A/M metallograph.
Co–29Cr–6Mo alloy samples (solid cylinders) were also HIP-
The etching protocols for the Ti–6Al–4V samples have been
annealed at 0.1 GPa for 4 h in Ar at 1200 ◦ C, and tensile
described in detail by Murr et al. (2009) while those for the
tested. All tensile tests were conducted at room temperature
Co–29Cr–6Mo alloy samples have been described by Gaytan
(∼20◦ C) utilizing a strain rate of ∼10−3 s−1 . Yield stress
et al. (2010).
measurements utilized the standard 0.2% engineering strain SEM analysis, including fractography for failed tensile
offset. Fracture surfaces for failed specimens were also specimens, employed a Hitachi S-4800 field emission (FE) SEM
examined by scanning electron microscopy (SEM). fitted with an EDAX energy-dispersive (X-ray) spectrometer
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Fig. 3 – Examples of solid and open-cellular, monolithic EBM built components of Ti–6Al–4V. (a) shows vertical built cylinder
(z) in build direction along z-axis and horizontal built cylinder (x, y) along x or y axis perpendicular to the build direction
(heavy arrow). (b) Foam and dode-thin reticulated mesh examples compared to solid cylinder (z). (c) Non-parallel view in (b)
showing 2 different density foam cubes at left, a solid cylindrical foam, an open core mesh cylinder, a similar mesh cylinder
with thin tube, and solid cylinder at right. Rockwell (HRC) values for solid vertical and horizontal cylinders are shown in (a).
(EDS) system; operated primarily at 20 kV in the secondary system operated at 300 kV, employing a goniometer-tilt stage,
electron emission mode. an EDS attachment, and a digital imaging system.
Solid, full-density samples were prepared for TEM analysis
by sectioning EBM-fabricated geometries (mostly cylinders)
3. Results and discussion
to prepare coupons which could be ground to a thickness
of ∼200 µm punched into 3 mm standard TEM samples 3.1. Comparison of solid Ti–6Al–4V and Co–29Cr–6Mo
which were mechanically dimpled and electropolished using alloy components
protocols described in Murr et al. (2009) for the Ti–6Al–4V
samples, and in Gaytan et al. (2010) for the Co–29Cr–6Mo Fig. 3 illustrates some examples of EBM fabricated solid
samples. The TEM was a Hitachi H-9500 high-resolution (full density) components (Fig. 3(a)) along with open-cellular
J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S 4 (2011) 1396–1411 1401
Fig. 11 – EBM-fabricated Ti–6Al–4V foam (a) and (b) and mesh (c) examples. (a) and (b) show views along diagonal and
normal to face (45◦ relative to (a)). Densities are noted.
and Co–29Cr–6Mo alloy open cellular structures represented It should be noted on comparing Figs. 17 and 18 that the
in Figs. 11–13. The Ti–6Al–4V mesh-strut microstructures Co–29Cr–6Mo alloy in Figs. 17(b) and 18(b) exhibit a similar
(Fig. 17(a)) are dominated by α′ -martensite plates corre- directional carbide microstructure to that shown for the EBM
sponding to the rapidly solidified (cooled) horizontal solid fabricated solid samples in Fig. 6, although not as extensive.
builds illustrated in Fig. 4(b), while the foam ligament ex- Note that the directional carbide columns in Figs. 17(b) and
ample shown in Fig. 18(a) exhibits a mixture of mainly α′ 18(b) form in build direction (arrow on the left in Figs. 17(b)
martensite, with some α-phase acicular platelets because and 18(b)).
of slightly different solidification rates. The α′ -martensite The Co–29Cr–6Mo alloy mesh-strut and foam-ligament
platelets are especially notable in contrast to the regular α- microstructures exhibit the same Cr23 C6 columnar precip-
phase acicular platelets for slower cooling solids as shown in itate architecture characteristic of the build process (beam
Fig. 5. scan geometry and corresponding, melt pool directional so-
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Fig. 12 – EBM-fabricated Co–29Cr–6Mo mesh examples in 2 views at 45◦ , (a) and (b) respectively. Densities are noted.
Fig. 13 – EBM-fabricated Co–29Cr–6Mo foam examples in 2 views at 45◦ , (a) and (b) respectively. Densities are noted.
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Ti-6Al-4V
5
4.1 4
4
3.4 3.5
HV (GPa)
0
SOLID (Z) SOLID (Z) HIP MESH FOAM 3.3. Knee replacement components and stress shielding
design strategies
Fig. 19 – Vickers microindentation hardness (HV)
comparisons for Ti–6Al–4V and Co–29Cr–6Mo solid and Fig. 20 illustrates two examples of contemporary, commer-
open-cellular (mesh and foam) components fabricated by cial, orthopaedic total knee replacements consisting of a
EBM. Co–29Cr–6Mo alloy femoral appliance (f ) and a Ti–6Al–4V tib-
ial stem appliance (t). These components are cemented using
acrylic cement onto the shaped bone segments with no stress
tation hardness (HV) measurements for the 3D reconstruc- shielding surface structure porosity. The left X-ray (Fig. 20(a))
tions in Figs. 17 and 18 are indicative of relatively high shows a right knee replacement with a slightly longer tibial
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Fig. 23 – Ti–6Al–4V EBM tibial knee stem monolithic prototype. (a) Dode-thin build element (Fig. 2(a)) creating a CAD model
with a solid rod core surrounded by a mesh. Note the enlarged mesh section insert on the left. (b) EBM prototype product
with a mesh density of ∼0.93 g/cm3 . (c) Magnified section in (b).
in Fig. 24 can be incorporated in femoral stem designs as these columnar precipitates dissolved and were replaced
described above, as well as the tibial stem concepts illustrated by a higher density of intrinsic stacking faults which
in Fig. 23. kept the hardness essentially constant, while there was
a slight drop in the yield stress. However, the UTS
increased by 20% while the elongation increased by 900%.
4. Summary and conclusions In contrast to the ASTM-F75 Co–29Cr–6Mo transplant
standard, the yield stress for the EBM-fabricated and HIPed
We have demonstrated that additive manufacturing using component increased by 30% while the elongation increased
electron beam melting can fabricate compatible, patient by ∼200%.
specific total knee implants: Co–29Cr–6Mo femoral appliances We measured the dynamic stiffness (Young’s modulus)
and Ti–6Al–4V tibial appliances consisting of monolithic, and density for Ti–6Al–4V and Co–29Cr–6Mo alloy mesh and
functional solid-mesh-foam components. In this study, we foam samples fabricated by EBM, and plotted these data
have compared characteristic microstructures for solid, as relative stiffness (E/Es ) versus relative density (ρ/ρs ) on
mesh, and foam Ti–6Al–4V prototypes. The Ti–6Al–4V log–log axes. A fitted line to the data resulted in a slope, n
solid EBM prototypes exhibit the α-phase, acicular platelet in Eq. (1) of 2.1. From this data plot, a stress shielding design
microstructures similar to commercial, wrought products, graph was constructed which permits Co–29Cr–6Mo and
while the mesh and foam prototypes exhibit α′ -martensitic Ti–6Al–4V mesh and foam implant prototypes to be fabricated
platelets or mixtures of α and α′ platelets which are for compatible bone stiffness in contrast to requisite
spatially smaller than the solid α-phase platelets, giving rise density.
to harder structures and correspondingly higher strengths.
In contrast, the EBM fabricated solid, mesh, and foam
Co–29Cr–6Mo prototypes all exhibited a directional, columnar Acknowledgments
Cr23 C6 precipitate architecture parallel to the EBM build
direction intermixed with some stacking faults in the fcc We are pleased to acknowledge the support of John Wooten
matrix. These columnar precipitates were spaced ∼2 µm of CalRam, Inc., Simi Valley, CA, and Ulf Ackelid of Arcam
within textured, directional grains. Following HIP-annealing AB, Sweden in specimen preparation and mechanical testing.
1410 J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S 4 (2011) 1396–1411
Thijs, L., et al., 2010. A study of the microstructural evolution Yang, S., et al., 2001. The design of scaffolds for use in tissue
during selective laser melting of Ti–6Al–4V. Acta Mater. 58, engineering, part I. Traditional factors. Tissue Eng. 7 (6),
3303–3312. 679–689.