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Design and fabrication of CoCrMo alloy based novel structures for load bearing
implants using laser engineered net shaping

Article in Materials Science and Engineering C · January 2010

DOI: 10.1016/j.msec.2009.08.006

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 Materials Science and Engineering C 30 (2010) 50–57

Contents lists available at ScienceDirect

Materials Science and Engineering C

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m s e c

Design and fabrication of CoCrMo alloy based novel structures for load bearing
implants using laser engineered net shaping
Félix A. España, Vamsi Krishna Balla, Susmita Bose, Amit Bandyopadhyay ⁎
W. M. Keck Biomedical Materials Research Laboratory, School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164-2920, USA

a r t i c l e i n f o a b s t r a c t

Article history: Designing load bearing implants with the desired mechanical and biological performance and to fabricate net
Received 14 November 2008 shape, functional implants with complex anatomical shapes is still a challenge. In addition, patient specific
Received in revised form 10 July 2009 load bearing implants with the possibilities of guided tissue regeneration are gaining significant interest in
Accepted 13 August 2009
orthopedics. Novel design approaches and fabrication technologies that can achieve balanced mechanical
Available online 26 August 2009
and functional performance in mono-block implants are necessary to accomplish these objectives. In this
Keywords:
article we give an overview of our novel design concepts for load bearing metal implants and demonstrate
Rapid manufacturing the manufacturing of unitized implant structures with and/or without porosity using laser engineered net
Laser engineered net shaping (LENS™) shaping (LENS™) — a solid freeform fabrication technique. We have fabricated porous metal implants with
Porous metals designed porosities up to 70 vol.% in various biomedical metals/alloys, such as Ti, Ti6Al4V, NiTi and CoCrMo,
Metal implants and tailored their effective modulus to suit the modulus of human cortical bone, thus eliminating stress-
Implant design shielding. Unitized structures with functionally graded CoCrMo alloy coating on porous Ti6Al4V alloy have
been fabricated using LENS™ to minimize wear induced osteolysis. Finally, this technology can also be used
to fabricate porous, net shape implants with functional gradation in structure and/or composition to mimic
natural bone. Since the LENS™ fabrication does not change the chemistry of the biocompatible alloys the
inherent in vitro and in vivo biocompatibility will remain the same and therefore, we have not provided any
biocompatibility results in this article. This article provide an insight into the important aspects of LENS™
fabrication and properties of CoCrMo alloy structures, which can potentially eliminate long standing
challenges in load bearing implants such as total hip prosthesis to increase their in vivo life time.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction reasons there is a considerable demand for improved THR's, and

similar load bearing implants, which can last longer in vivo.
Metallic biomaterials are extremely successful in restoring lost In order to increase the in vivo lifetime of metal implants, one can
functions of human bone under high loads. However, metals are (i) decrease its effective modulus to match that of bone, and (ii)
bioinert and have a considerably higher stiffness than natural bone increase the interfacial bond between living cells and implant
which significantly reduces the implant's in vivo lifetime. For example, materials via compositional or structural modification. Use of porous
total hip replacement (THR) surgeries are being performed more on metals in place of fully dense material can effectively reduce the
younger patients below the age of sixty, which expose the implant to modulus mismatch [1–3]. Also, the interconnected porosity increases
greater mechanical stress over a longer period of time due to their the bone-implant interfacial bond by bone ingrowth through the
active lifestyle. Short life of current THR implants, between 7 and pores. Several processing routes have been used to fabricate surface
12 years, is generally due to the aseptic loosening of the implant, treated or fully porous metals for biomedical applications. In
which occurs due to (i) mismatch of the Young's modulus between conventionally sintered metals [4–7] porosity characteristics such as
bone (10–30 GPa) and metallic implant materials (110 GPa for Ti pore size, shape, volume fraction, and distribution are difficult to
and 248 GPa for CoCrMo alloy) leading to stress-shielding, (ii) poor control, which have major influence on mechanical and biological
interfacial bond between the host tissue and the implant due to properties. Other fabrication techniques that use foaming agents or
bioinert surface, (iii) wear induced osteolysis and aseptic loosening in molten metal suffer from typical limitations such as contamination,
metal-on-polymer implants, and (iv) absence of high recoverable impurity phases and limited part geometries. Overall, the parts fabri-
strain (~ 2%) as well as hysteresis similar to natural bone. For these cated using above processes usually suffer from loss of physical pro-
perties due to stress concentrations at the porous interface,
microstructure changes, and surface contamination [4,5,7]. Another
⁎ Corresponding author. Fax: +1 509 335 4662. serious concern limiting the life of THR is relatively high wear rate of
E-mail address: [email protected] (A. Bandyopadhyay). ultra-high-molecular-weight polyethylene (UHMWPE) liner leading

0928-4931/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.msec.2009.08.006
 F.A. España et al. / Materials Science and Engineering C 30 (2010) 50–57 51

to osteolysis and aseptic loosening [8]. In the past, ceramic coatings real hurdle. Functional implants with these complex designs can be
have been proposed, as being wear-resistant and a metal ion release fabricated using layered manufacturing processes, generally known
barrier for THR. These coatings were obtained using different vapor as solid freeform fabrication (SFF) and one such process is laser
deposition techniques, such as physical vapor deposition, ion engineered net shaping (LENS™). This process uses a focused laser
implantation, sputtering and the coatings consisted of diamond-like beam as a heat source to melt metallic powder and create a solid,
carbon [9,10] or nitrides [11,12]. These coatings have found little three-dimensional object. A schematic representation of the LENS™
application in the field of THR due to their inherent brittleness process is shown in Fig. 2. Initially, a three-dimensional model of a
and catastrophic fracture possibilities. Therefore, there is a growing component to be built is generated using CAD, subsequently a
interest in wear-resistant metal/alloy coatings for THR because of computer program slices the model into a number of horizontal
their excellent toughness coupled with high wear resistance. It is cross-sections or layers. These cross-sections are sequentially
clear from the foregoing discussion that improved fixation and created on a substrate producing a three-dimensional object.
increased longevity are still important performance criteria in the More detailed description of the process is provided elsewhere
development of orthopedic prostheses, which mandates the devel- [2]. Being a CAD and layer based manufacturing process LENS™
opment of innovative designs and use of advanced manufacturing gives significant advantage over conventional manufacturing
techniques. methods in terms of tailoring microstructure, shape, size and
internal architectures particularly of porous structures in one
2. Novel macro/micro structural design for load bearing implants operation by controlling different process parameters. Multiple
powder feeding and closed loop melt pool control systems facilitate
The need for adequate mechanical and functional properties the fabrication of components with functional gradient in compo-
coupled with manufacturing flexibility for a wide range of metallic sition and/or porosity across the section. Since the fabrication is
implant materials demands the use of novel designs. Innovative carried out in a protective atmosphere with oxygen content less
designs such as functionally graded acetabular shells with open than 10 ppm, LENS™ processed materials retain the purity of feed-
porosity on one side to improve cell–material interactions and a hard stock powder, which is extremely important during processing of
coating on the other side (in contact with femoral head) to increase materials for biomedical applications. LENS™ process involves high
the wear resistance, can significantly improve the implant's in vivo solidification cooling rates (103 to 105 K/s) leading to several
life by completely eliminating the need for acetabular liners. By microstructural benefits [16]. Many metallic, intermetallic, ceramic,
eliminating the liner, the diameter of femoral head can be increased, and composite powders have been successfully processed using
which in turn provides greater maneuverability and stability for the LENS™ [17–20].
implant assembly. A schematic of such gradient structure is shown
in Fig. 1A. Similarly, graded structures with gradual increase in the 3. Implant manufacturing
concentration of bioactive calcium phosphate based ceramic from
metallic implant's core to the surface can significantly increase 3.1. Net shape porous implants
osseoconductivity, while simultaneously reducing the interfacial
problems such delamination during fabrication or in service. While a Fig. 3 shows the two types of porosity, namely inter-particle
wear-resistant alloy coating on metal substrates seems plausible, porosity and tool path based porosity that can be introduced in the
there is only one metallic alloy combination, i.e. CoCrMo and Ti6Al4V, parts using LENS™. The extent of powder melting in each track/scan
suitable for surgical implant, which shows metallurgical incompat- decides the achievable porosity in the final part depending on laser
ibility [13]. Although functionally graded coatings (FGCs) can over- energy input, which can be controlled by changing LENS™ process
come metallurgical incompatibility, it is difficult, if not impossible, to parameters such as laser power (P), scan spacing (h), powder feed
fabricate net shape implants/structures with spatial gradation in rate, laser scan speed (v) and Z-increment or layer thickness (t). Since
composition and structure with conventional processing routes. The the parts are made via layer wise deposition, and each layer consists of
uniform structural/compositional change across the interface in a number of consecutive overlapping tracks/scans, the final density of
FGCs provides unique functionality and performance for biomedical a LENS™ processed part can be considered as an average of the
applications [14,15]. For example, implants with gradients in density of each track/scan. The total energy input per volume of each
porosity and pore sizes, as shown in Fig. 1B, that can allow on one track/scan (E, J/mm3) as a function of processing parameters can be
side of the implant high vascularization and direct osteogenesis, evaluated from [21]:
while promoting osteochondral ossification on the other, are
appealing in terms of reproducing multiple tissues and tissue P
interfaces on the same implant. Porosity is not always beneficial for E= ð1Þ
v⋅h⋅t
:
THR, as it can significantly decrease the wear resistance of biomedical
metals/alloys. While fully dense CoCrMo alloy based implants can
provide the best wear resistance, its high stiffness (248 GPa) can At appropriate LENS™ process parameters one can achieve
pose problems due to stress-shielding. Therefore, the only way to optimal lowest energy input ensuring lower working temperatures
reduce the stiffness of CoCrMo alloy without sacrificing its wear and small amount of liquid phase around the powder particles due
resistance is to fabricate an implant with fully dense outer surface to partial melting of the powder. These surface melted powders join
and isolated/interconnected porosity inside. Finally, if one implant together leaving some inter-particle porosity. Fig. 3 shows the
with various sections having different internal/external macrostruc- formation of porosity in each track. Particle bonding in this case is
tures, such as fully dense, fully porous, and porous core with solid a direct result of localized melting and resolidification as against
walls, can be designed and fabricated, then the implant can posses solid state sintering in powder metallurgical route. Therefore, the
site specific functions at different location on the same implant. An inherent brittleness associated with solid state sintered metal
example of this functionally designed hip stem is shown schemat- powders is completely eliminated, potentially enhancing implant's
ically in Fig. 1C. fatigue life. Structures with different porosity parameters and
The above designs enable implants with designed macro- and internal architecture with designed gradient across the part can
microporosity to achieve desired mechanical and functional perfor- also be fabricated by optimizing the distance between two
mance. Although such innovative implant designs can potentially successive metal roads (laser scans) and the thickness of each
triple the in vivo life of load bearing implants, fabricating them is a metal layer. Moreover, by changing the deposition angles of laser
52 F.A. España et al. / Materials Science and Engineering C 30 (2010) 50–57

Fig. 1. Schematic showing novel implant designs.

scans for each layer, the tool path based pores can be oriented layer 3.2. Functionally graded/unitized structures
by layer leading to a three-dimensional interconnected porosity.
Fig. 4 shows typical porous titanium samples and actual hip stems Independently controllable multiple powder feeders in LENS™
produced via LENS™. These samples show the net shape fabrication enable variation of composition and porosity simultaneously in one
capability of LENS™. operation to manufacture novel implant structures. Functionally
 F.A. España et al. / Materials Science and Engineering C 30 (2010) 50–57 53

Fig. 2. Schematic depiction of LENS™ process.

graded structures with hard and wear-resistant CoCrMo alloy coating time of load bearing metal implants. From these works it is apparent
on porous Ti6Al4V alloy with metallurgically sound interface have that LENS™ can be used to manufacture a variety of load bearing
been produced using LENS™ [22]. In vitro biocompatibility study implants with tailored microstructures and compositions while
showed that these coatings were non-toxic and biocompatible [22]. maintaining the size and the shape for specific applications or
Composition gradation in the transition region was achieved by patients.
gradually increasing the feed rate for CoCrMo alloy and accordingly
decreasing the feed rate of Ti6Al4V alloy powder over 5–7 layers of 4. Case study: CoCrMo alloy structures
deposition. Elimination of intermetallic compounds in these coatings,
due to rapid cooling rates, is beneficial in terms of better wear CoCrMo alloy powder, Stellite® 21, (Stellite Coatings, Goshen, IN,
resistance and biocompatibility [23]. Gradient coatings with 86% USA) with particle size between 45 and 150 μm was used in this study.
CoCrMo in the top surface showed ~184% increase in surface hardness. The nominal chemical composition (wt.%) of CoCrMo alloy powder,
Moreover, the porosity on the Ti6Al4V alloy side, which will be in conforming to ASTM F75, was 27 Cr, 5.5 Mo, 2.75 Ni, 15 Fe, 0.25 C, 1
contact with the bone, can improve bone tissue ingrowth [3,5] and Mn, 1.5 Si and balance Co. The substrates used were rolled
hard coating on the other side increases the wear resistance of the commercially pure Ti plates of 3 mm thickness (President Titanium
structure in contact with CoCrMo femoral heads. Co., MA, USA). LENS™-750 (Optomec Inc. Albuquerque, NM, USA)
LENS™ also has the capability to fabricate two separate parts with 500 W Nd-YAG laser system was used to fabricate porous
simultaneously in one operation, to make unitized structures, which CoCrMo structures. Two laser power levels of 200 and 250 W were
can potentially eliminate (i) interfacial problems associated with used to partially melt the alloy powder during the deposition process
sharp interface between conventionally assembled parts, and (ii) to create porous structures. In this work, scan speeds of 15 and
precision machining and assembling of the components fabricated 20 mm/s and powder feed rates of 40, 50, and 60 g/min were used to
separately by conventional routes. For example consider a typical dog study their influence on the porosity. As stated earlier, porosity
bone implant, as shown in Fig. 5A, which consists of two parts namely significantly reduces the wear resistance of CoCrMo alloy based
porous sleeve, to enhance osseointegration, and solid core to support implants, which are used for self-bearing applications due to its
the mechanical loads. Such implants conventionally manufactured outstanding wear resistance. However, one concern about CoCrMo
and assembled usually suffer from low fatigue strength due to sharp alloys is its high stiffness. Therefore, methodologies to reduce CoCrMo
interface between the porous sleeve and the fully dense core. Using alloy stiffness while maintaining its wear resistance are extremely
LENS™ we have manufactured these two parts simultaneously in one important. The present CoCrMo alloy samples contain fully dense
step making the implant a unitized structure, shown in Fig. 5B, outer surface to retain its inherent wear resistance and a porous core
without sharp interface, which can potentially increase the in vivo life inside the structure, which reduces the effective stiffness of the

Fig. 3. Porosity formation during LENS™ processing.

54 F.A. España et al. / Materials Science and Engineering C 30 (2010) 50–57

Fig. 5. Typical dog bone implant. (A) CAD model. (B) LENS™ processed porous sleeve
(left) and solid core (middle), which require further finishing and assembly. Unitized
Fig. 4. LENS™ processed porous titanium structures. (A) Samples with total porosity
structure (right) with porous sleeve and fully dense core can be fabricated in one step
>50 vol.% are fabricated using tool path based porosity. (B) Net shape, functional hip
using LENS™.
stems with designed porosity fabricated using LENS™.

structure to match that of human cortical bone. Dense outer surface which was derived from human fetal bone tissue [24]. OPC1 cells were
was fabricated by decreasing the scan speed, by 5 mm/s, during seeded onto the samples placed in 12-well plates. Initial cell density
deposition of outer surface/contour. Fig. 6 shows the cross-sectional was 5.0 × 104 cells per well. A 1 ml aliquot of McCoy's 5A medium
image of such CoCrMo alloy structures. (enriched with 5% fetal bovine serum and 5% bovine calf serum, and
Cylindrical samples with 7 mm diameter were fabricated for com- supplemented with 4 μg per ml of fungizone) was added to each well.
pression testing and microstructural evaluation. Bulk density, which Cultures were maintained at 37 °C under an atmosphere of 5% CO2.
includes both open and closed pores, of the samples was determined
by measuring physical dimensions and mass of the samples. Apparent
density, which includes closed pores, was also measured. The fraction
of open and closed pores in the samples was calculated from the bulk
and apparent densities. Microstructural studies were performed using
light microscope and field emission scanning electron microscope
(FESEM, FEI – Quanta 200F). Polished specimens were electrolytically
etched with 5% HCl aqueous solution at 3 V for about 10 s. Constituent
phases in the laser processed samples were identified using a Siemens
D 500 Kristalloflex diffractometer with Cu Kα radiation (1.54056 Å)
at 20 kV between the 2θ range of 20 and 80°, and compared with
those of as-received powder. Three samples corresponding to each
density were compression tested using servo hydraulic axial/torsion
materials test system machine with 250 kN capacity at a strain rate
of 10− 3 s− 1. Polytetrafluoroethylene (PTFE) was used as a lubricant
between the sample and compression tools to reduce friction. Young's
modulus and compression strength was determined from the stress-
strain plots derived from load-displacement data recorded during
compression testing. Vicker's microhardness measurements (Leco, M-
400G3 model) were performed on the laser processed CoCrMo alloy
samples using 200 g load for 15 s. An average value of 10 measure-
ments on each sample was reported.
Samples for in vitro biocompatibility test were sterilized by
autoclaving at 121 °C for 20 min. In this study the cells used were Fig. 6. Typical LENS™ processed CoCrMo alloy sample with fully dense outer wall and
an immortalized, cloned osteoblastic precursor cell line 1 (OPC1), porous matrix inside. The relative bulk density of this structure was 82%.
 F.A. España et al. / Materials Science and Engineering C 30 (2010) 50–57 55

Table 1 formazan crystals. Then 100 μl of the resulting supernatant was

Influence of laser parameters on the porosity of CoCrMo alloy samples. transferred into a 96-well plate, and read by a plate reader at 570 nm.
LENS™ Scan Powder Laser Bulk Comments
parameter speed, feed rate, power, density,
mm/s g/min W % 4.1. Porosity characteristics
Power 200 15 60 ⁎⁎⁎ 82.5 Porosity decreases with
250 87.5 increasing power Relative density of laser processed porous CoCrMo alloy samples
Scan 15 ⁎⁎⁎ 50 250 88.4 Porosity increases with
varied from 81% to 90% depending on laser processing parameters.
speed 20 87.0 increasing scan speed
Powder 40 20 ⁎⁎⁎ 250 90.4 Porosity increases with
As-processed samples showed rough surface which can enhance the
feed 60 88.2 increasing powder feed long-term stability of the implants by providing anchorage for
rate rate biological fixation and by enabling stresses to be transferred from the
*** No results. implant to the bone. However, for wear resistance applications final
finishing is required. Experimental data related to the influence of
Medium was changed every 2–3 days for the duration of the laser parameters on the porosity of CoCrMo alloy samples, as shown
experiment. The MTT (Sigma, St. Louis, MO) solution of 5 mg ml−1 in Table 1, indicate that total porosity of CoCrMo alloy samples can be
was prepared by dissolving MTT in PBS, and filter sterilized. The MTT tailored by changing the LENS™ processing parameters.
was diluted (50 μl into 450 μl) in serum-free, phenol red-free The porosity decreased with a decrease in the scan speed, powder
Dulbeco's minimum essential medium. Then 500 μl of diluted MTT feed rate and by increasing the laser power. The working tempera-
solution was added to each sample in 12-well plates. After 2 h of tures decreases with decreasing laser energy input (by decreasing
incubation, 500 μl of solubilization solution made up of 10% Tri- laser power and/or increasing the scan speed or feed rate) leading to a
ton X-100, 0.1 N HCl and isopropanol was added to dissolve the partial melting of powders during LENS™ deposition. These partially

Fig. 7. (A) X-ray diffraction pattern of laser processed structures and as-received CoCrMo alloy powder. (B) Microstructure of as-received CoCrMo alloy powder. (C) Microstructure
of laser processed CoCrMo alloy.
56 F.A. España et al. / Materials Science and Engineering C 30 (2010) 50–57

Fig. 8. Influence of porosity on the Young's modulus of laser processed CoCrMo alloy samples.

melted powders join together in the presence of the liquid metal at leading to relatively less amount of liquid phase around the metal
the particle–particle interfaces, leaving some inter-particle porosity. powders. As a result, the particle rearrangement, which is considered
On the other hand, increasing the energy input, by increasing the laser responsible for high sintered density in liquid phase sintering, will be
power, increases the working temperatures and consequently melts less in this case resulting in high porosity in the samples processed
the powder completely leading to a dense deposit/layer. In addition, at high scanning speeds. Finally, in general, high porosity samples
at high working temperatures the flow of liquid metal to fill any were achieved as the powder feed rate was increased while keeping
residual inter-particle pores becomes easier and promotes higher the laser power and scan speed constant. As the powder feed rate
densification than at low working temperatures. Increasing the pow- is increased there is more volume of powder in the laser–material
der feed rate increases the volume of powder in the laser–materials interaction zone. This will decrease the laser energy density of the
interaction zone, i.e., thicker tracks, leading to a decrease in the laser powder leading to only partially melted material and then conse-
energy input. The low energy absorbed by the powder particles quently to high porosity samples. Similar observations were made in
results in partial melting of the powder, consequently high porosity in laser processed Ti samples [2].
the samples. At constant powder feed rate and scan speed, decreasing Vicker's microhardness measurements of LENS™ processed po-
the laser power from 250 W to 200 W, resulted in high porosity in the rous CoCrMo alloy samples fabricated under various processing
samples. In the same manner, porosity increased as the scan speed conditions indicated an average hardness of 361 ± 11 Hv. X-ray dif-
was increased and other parameters being held constant. This is fraction results, as shown in Fig. 7A, of laser processed CoCrMo alloy
attributed to the fact that as the scan speed is increased, the inter- samples show that all major peaks correspond to as-received powder.
action time between the powder and laser is reduced. Therefore, the However, presence of (102) and (101) in laser processed in place of
instantaneous laser energy absorbed by the powder also decreases (200) and (220) of as-received powder indicate the presence of some

Fig. 9. Compressive strength of laser processed CoCrMo alloy samples as a function of sample porosity.
 F.A. España et al. / Materials Science and Engineering C 30 (2010) 50–57 57

texture i.e., solidification in preferred direction. Preferential grain can potentially eliminate the long standing issues such as stress-
orientation in LENS™ processed materials is common [25] due to the shielding, poor interfacial bond between the host tissue and the
rapid heat loss through the substrate, as observed in the present work. implant, and wear induced bone loss, in load bearing implants to
Moreover, the microstructural study, as shown in Fig. 7B and C, increase their in vivo life time. Porosities, pore characteristics and
showed thicker carbide networks in laser processed sample com- mechanical properties of laser processed structures can be tailored to
pared to that observed in as-received powder. The additional peak, suite various biomedical applications by changing LENS™ process
Cr7C3 (511), in laser processed sample could also be due to thicker parameters. Moreover, LENS™ processing retains inherent biocom-
carbide network present in this sample. The variations in carbide patibility of feed stock materials. Under present experimental
network are presumably due to variations in cooling rates during laser conditions, the average total porosity of CoCrMo alloy samples with
processing. solid wall and porous core can be varied in the range of 10% to 18%
with a modulus between 33 to 43 GPa.
4.2. Mechanical and biological properties

Mechanical properties of laser processed porous CoCrMo alloy Acknowledgements

structures are shown in Figs. 8 and 9. The data indicates that the
Young's modulus of the laser processed porous samples can be varied Authors would like to acknowledge the financial support from the
between 33 and 43 GPa by changing the LENS™ process parameters. Office of Naval Research (grant no. N00014-1-05-0583) and the
This is a huge improvement when compared to the wrought CoCrMo National Science Foundation (grant no. CMMI 0728348). Authors
alloy with a modulus of 248 GPa. The modulus of porous CoCrMo alloy would also like to acknowledge W. M. Keck Foundation's financial
is close to that of natural bone which has a range of 3 to 20 GPa. The support to establish the Biomedical Materials Research Lab at WSU.
elastic modulus varied depending on porosity of the structures and
modulus decreased with the increasing pore fraction. This trend is
intuitive as the samples become less stiff and more easily deformed at References
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Application of LENS™ to fabricate novel porous and unitized
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structures with functional gradation in composition and/or porosity

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