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Developments in Titanium Overview

Engineered Porous Metals for


Implants
B. Vamsi Krishna, Weichang Xue, Susmita Bose, and Amit Bandyopadhyay

Interest is significant in patient-spe- long-term anchorage or biological fixa-


cific implants with the possibility of How would you… tion of the implant.1,2
guided tissue regeneration, particular- …describe the overall significance Conventional powder metallurgical
ly for load-bearing implants. For such of this paper? processing has been used to fabricate
implants to succeed, novel design ap- The lifetimes of load-bearing surface-treated or fully porous metals3–8
proaches and fabrication technologies metal implants in the human body for biomedical applications. These con-
can be increased significantly
that can achieve balanced mechanical via compositional and structural ventionally sintered metals are often
and functional performance in the im- modifications of the implants. very brittle and pore size, shape, vol-
plants are necessary. This article is fo- Advanced technologies are needed to ume fraction, and distribution are dif-
manufacture these advanced designs.
cused on porous load-bearing implants ficult to control. These factors all have
This article discusses properties of
with tailored micro- as well as macro- porous metals and the application a major influence on mechanical and
structures using laser-engineered net of the laser-engineered net shaping biological properties. Other fabrication
shaping (LENS“), a solid freeform process to manufacture unitized techniques that use foaming agents or
structures of load-bearing metal
fabrication or rapid prototyping tech- implants.
molten metal suffer from typical limi-
nique that can be used to manufacture tations such as contamination, impurity
patient-specific implants. This review …describe this work to a phases, limited and predetermined part
materials science and engineering
provides an insight into LENS, some professional with no experience in geometries, and limited control over the
properties of porous metals, and the your technical specialty? size, shape, and distribution of porosi-
potential applications of this process to A mismatch of Young’s modulus and ty. In addition, to mimic multiple tis-
fabricate unitized structures which can a weak interfacial bond between sues and tissue interfaces on the same
eliminate longstanding challenges in bone and metallic implant materials implant, implants with gradients in po-
are the two major concerns for
load-bearing implants to increase their current load-bearing implants, rosity and pore sizes that will allow on
in-vivo lifetime, such as in a total hip which reduce their effective lifetime one side of the implant high vascular-
prosthesis. when implanted. Implants with ization and direct osteogenesis, while
functional gradation in porosity
promoting osteochondral ossification
INTRODUCTION and/or composition can potentially
reduce these problems—a topic on the other, are difficult to manufac-
The major drawbacks of current that is discussed in this article in ture using those techniques.
load-bearing implants, reducing their reference to how to manufacture such Further, the relatively higher wear
structures, as well.
in-vivo life, are a mismatch of Young’s rate of traditional hip replacements
modulus and a weak interfacial bond …describe this work to a with ultrahigh-molecular-weight poly-
between bone and metallic implant ma- layperson? ethylene liner is a cause of serious con-
terials. In addition, wear-induced oste- Solid metal bone implants are stiffer cern due to osteolysis and aseptic loos-
than bone. Because of this higher
olysis and aseptic loosening in metal- stiffness, bone becomes osteoporotic ening, which is one of the major fac-
on-polymer implants, and absence of surrounding the implanted area. tors limiting the life of hip prostheses.9
high recoverable strain (~2%) as well Moreover, the implants become Innovative designs such as functionally
as hysteresis in biocompatible metals, loose with time and cause severe graded acetabular shells with open po-
pain, which then requires surgical
similar to natural bone, are other fac- intervention. Engineered porous rosity on one side (in contact with the
tors that limit the in-vivo life of im- metals can be used to reduce this bone) to improve cell-material interac-
plants. One consideration to achieve a stiffness mismatch between bone and tions and a hard coating on the other
implant, and also provide pathways
strong interfacial bond and also to re- side (in contact with femoral head) to
for tissue ingrowth through the pores.
duce modulus mismatch has been the Therefore, porous implants have the increase the wear resistance can signif-
development of implants with porous potential to reduce bone loss in the icantly improve the implant’s in-vivo
metals. Use of porous metals can ef- surrounding areas when implanted life by completely eliminating the need
and also loosening of implants. Thus
fectively reduce the modulus mis- the lifetime of these porous metallic
for acetabular liners. While a wear-re-
match and provide pathways for bone implants can be significantly higher. sistant alloy coating on metal substrates
in-growth through the pores for stable seems plausible, there is only one me-

2008 May • JOM www.tms.org/jom.html 45


tallic alloy combination (i.e., Co-Cr-
Mo and Ti-6Al-4V) suitable for surgi-
cal implants, which shows metallurgi-
cal incompatibility.10 Although func-
tionally graded coatings can overcome
metallurgical incompatibility, it is diffi-
cult, if not impossible, to fabricate net-
shaped implants/structures with spatial
gradation in composition and structure
with conventional processing routes.
LASER-ENGINEERED NET Figure 2. The formation of porosity during LENS processing.
SHAPING
Over the past few years, direct fab-
rication of metallic components using a layer of material to be deposited. Fi- than 10 ppm, LENS-processed materi-
the solid freeform fabrication route nally, this procedure is repeated many als retain the purity of feedstock pow-
from computer-aided design (CAD) times along the Z-direction (i.e., height) der, which is extremely important dur-
files has been shown to be a viable and until the entire object represented in the ing processing of materials for biomed-
promising near-net shape manufactur- three-dimensional CAD model is pro- ical applications. The LENS process in-
ing technology. One such process is la- duced on the substrate, which is a solid volves high solidification cooling rates
ser-engineered net shaping (LENS™), or tailored-porosity object. Many me- (103 to 105 K/s) leading to several mi-
which involves complete melting of tallic, intermetallic, ceramic, and com- crostructural benefits14 such as suppres-
metal/alloy powders using a high-pow- posite powders have been successfully sion of diffusion-controlled solid-state
er laser beam as the heating source for processed using LENS.11–13 phase transformations, formation of
fabrication of near-net shape functional Because it is a CAD and layer-based supersaturated solutions and nonequi-
parts. A schematic of the LENS pro- manufacturing process, LENS has a librium phases, formation of extremely
cess is shown in Figure 1. The process significant advantage over convention- fine, refined microstructures with little
uses an neodymium-doped yttrium alu- al manufacturing methods in terms of elemental segregation, and formation
minium garnet laser, up to 4 kW power, tailoring microstructure, shape, size, of very fine second-phase particles (in-
focused onto a metal substrate to create and internal architectures, particularly clusions, carbides, etc.). Finally, it is a
a molten metal pool on the substrate. of porous structures, in one operation reliable process that can be applied for
Metal powder is then injected into the by controlling different process pa- a direct low-volume manufacturing.
metal pool, which melts and solidifies. rameters. Multiple powder feeding and
Net-Shaped Functional Porous
The substrate is then scanned relative to closed-loop melt pool control systems
Implants
the deposition head to write a metal line facilitate fabrication of materials with
with a finite width and thickness. Ras- functional gradient in composition and/ Novel design concepts15 have been
tering of the part back and forth to cre- or porosity across the section. Since the applied to make complex-shaped func-
ate consecutive overlapping tracks and fabrication is carried out in a protective tional implants with designed and func-
fill material in the desired area allows atmosphere with oxygen content less tionally graded interconnected porosity,
to suit natural bone, using LENS. Two
types of porosity, namely inter-particle
porosity and tool-path-based porosity,
can be introduced into the parts by con-
trolling LENS process parameters such
as laser power (P), scan spacing (h),
powder feed rate, laser scan speed (v),
and Z-increment or layer thickness (t).
Since the parts are made via layer-wise
deposition, and each layer consists of
a number of consecutive overlapping
tracks/scans, the final density of a
LENS processed part can be considered
as an average of the density of each
track/scan. The extent of powder melt-
ing in each track/scan depends on laser
energy input and decides the achievable
Figure 1. A schematic porosity in the final part. The total ener-
representation of LENS. gy input per volume of each track/scan
(E) as a function of processing param-

46 www.tms.org/jom.html JOM • May 2008


eters can be evaluated from16
P
E (1)
v–h–t
At appropriate LENS process pa-
rameters one can achieve the optimal
lowest energy input that ensures low- Figure 4. The modulus
er working temperatures and a small of porous samples pro-
cessed using LENS.
amount of liquid phase around the The graph is construct-
powder particles due to the partial melt- ed based on the data
ing of powder. These surface-melted from References 15,
17, and 18.
powders join together in the presence
of liquid metal at the particle-particle
interfaces, leaving some inter-particle
porosity. Figure 2 shows the forma-
tion of porosity in each track. Particle can also be fabricated by optimizing the total porosities in various biomedical
bonding in this case is a direct result of distance between two successive metal materials such as pure Ti, Ti-6Al-4V,
localized melting and resolidification roads (laser scans) and the thickness of and NiTi alloys have been fabricated
as against solid-state sintering in the each metal layer. Moreover, by chang- using LENS15,17,18 with laser power be-
powder metallurgical route. Therefore, ing the deposition angles of laser scans tween 150 W and 300 W, scan speeds
the inherent brittleness associated with for each layer, the tool path based pores between 5 mm/s and 25 mm/s, powder
solid-state sintered metal powders is can be oriented layer by layer leading feed rate in the range of 15 g/min. and
completely eliminated, potentially en- to a three-dimensional (3-D) intercon- 38 g/min., and scan spacing between
hancing the implant properties such as nected porosity. The individual laser 0.76 mm and 1.27 mm. Figure 3 shows
fatigue. Structures with different poros- tracks/scans can also have inter-particle typical porous titanium samples and
ity parameters and internal architecture porosity depending on the laser energy actual hip stems produced via LENS at
with a designed gradient across the part input. Porous samples with different Washington State University.
The experimental data shown in Fig-
ure 4 indicate that samples with varying
amounts of total porosity can be made
using LENS by changing processing
parameters.15,17,18 Moreover, the modu-
lus of laser-processed materials can be
tailored between 2 GPa and 90 GPa to
match that of natural bone by introduc-
a ing total porosities in the range of 10
vol.% and 60 vol.%. Similarly, porous
NiTi alloy samples with 12–36% po-
rosity exhibit low Young’s modulus
between 2–18 GPa as well as high
compressive strength and up to 4% re-
coverable strain.18 These porous metals
with modulus similar to bone and open
porosity in the range of 53% to 72%
of total porosity not only reduce the
stress-shielding but also have potential
to significantly improve bone cell-im-
plant interaction. An in-vitro cell-mate-
rials interactions study has been carried
out on laser-processed porous titanium
samples.19
Porous titanium samples enhanced
bone cell proliferation by forming
more extracellular matrix and a high
b level of alkaline phosphates expres-
Figure 3. (a) LENS-processed porous titanium structures. Group I: samples with residual sion19 than observed in fully dense tita-
porosity (<40 vol.%), Group II: samples with tool path based porosity 50 vol. %, Group
III: samples with internal architecture. (b) Net shape, functional hip stems fabricated using nium, which can accelerate the integra-
LENS“. tion of a porous implant with host bone
tissue. A critical pore size of 200 Mm

2008 May • JOM www.tms.org/jom.html 47


unitized structures with functional gra-
dation in composition and/or porosity
Unmelted Ti-6Al-4V Particles can potentially eliminate the longstand-
ing issues such as stress-shielding, poor
interfacial bond between the host tis-
sue and the implant, and wear-induced
bone loss in load-bearing implants to
Alloy
Ti-6Al-4V Alloy

increase the in-vivo lifetime.


Ti-6Al-4V

ACKNOWLEDGEMENTS
Increasing Co-Cr-Mo Alloy Concentration
0.6 mm The authors acknowledge financial
Figure 5. Typical microstructures of laser-processed Co-Cr-Mo graded coating on porous support from the W.M. Keck Foun-
Ti-6Al-4V alloy.20 dation, the Office of Naval Research
(Grant #N00014-1-05-0583), and the
National Science Foundation (Grant
or higher has been identified for cell porous layers. The composition in the #CMMI-0600739).
in-growth into porous samples. It was transition region of the gradient struc- References
also shown15 that by changing the pore ture was varied from 100% Ti-6Al-4V
1. R.M. Pillar, J. Biomed. Mater. Res.—Appl. Biomater.,
shape from spherical to more irregular, alloy at the first layer to various con- 21 (A1) (1987), pp. 1–33.
one can reduce the modulus of these centrations of Co-Cr-Mo alloy at the 2. A.J.T. Clemow et al., J. Biomed. Mater. Res., 15
porous samples. Therefore, LENS pro- top layer over 5–6 layers. Because of (1981), pp. 73–82.
3. I.H. Oh et al., Scripta Mater., 49 (2003), pp. 1197–
vides more flexibility for designers to metallurgical incompatibility a 100% 1202.
tailor the modulus of samples with- Co-Cr-Mo transition from Ti-6Al-4V 4. R.M. Pillar, Int. J. Powder Metallurgy, 34 (8) (1998),
out changing their bulk density or to- could not be made. However, crack- pp. 33–46.
5. C.E. Wen et al., Scripta Mater., 45 (2001), pp. 1147–
tal pore volume. It is apparent that this free structures containing up to 86% 1153.
versatility will allow the fabrication of Co-Cr-Mo on one side of the structure 6. K. Otsuka and C.M. Wayman, Shape Memory Ma-
implants with different porosities, pore and 100% porous Ti-6Al-4V alloy on terials (Cambridge, U.K.: Cambridge University Press,
1998).
sizes, and mechanical properties that the other side have been fabricated with 7. J.C. Hey and A.P. Jardine, Mater. Sci. Eng. A., 188
can mimic the complex architecture of excellent reproducibility. The typical (1994), pp. 291–300.
bone-specific sites to optimize bone tis- microstructure of such a gradient struc- 8. W.U. Shuilin et al., Acta Mater., 55 (2007), pp. 3437–
3451.
sue regeneration. ture is shown in Figure 5.20 9. H.G. Willert, H. Bertram, and G.H. Buchhorn, Clin.
Extremely high cooling rates dur- Orthop. Relat. Res., 258 (1990), pp. 95–107.
Functionally Graded Structures 10. Alloy Phase Diagrams: ASM Handbook, vol. 3 (Ma-
ing laser processing prevented the for-
terials Park, OH: ASM International, 1992).
The uniform and gradual changes mation of intermetallic compounds by 11. B. Vamsi Krishna, Susmita Bose, and Amit Ban-
in composition, crystallinity, and/or limiting the interaction time between dyopadhyay, Metallurgical and Materials Transactions
grain structure across the interface of metallurgically incompatible titanium A, 38A (2007) pp. 1096–1103.
12. B. Vamsi Krishna, Susmita Bose, and Amit Ban-
functionally gradient materials provide and cobalt at high temperatures. The dyopadhyay, International Journal of Applied Ceramic
unique functionality and performance absence of intermetallic compounds Technology (on-line 29 February 2008), doi:10.1111/
for medical applications. As stated ear- in these structures is very important to j.1744-7402.2008.02202.x.
13. W. Liu and J.N. DuPont, Scripta Mater., 48 (2003),
lier, unitized structures such as func- retain wear resistance and biocompat- pp. 1337–1342.
tionally graded acetabular shells with ibility. As can be seen from the micro- 14. W. Hofmeister et al., JOM, 53 (9) (2001), pp. 30–
open porosity on one side and a hard structure, the temperature fluctuations 34.
15. B. Vamsi Krishna, Susmita Bose, and Amit Bandyo-
coating on the other side significantly in the liquid metal pool due to chang- padhyay, Acta Biomaterialia, 3 (2007), pp. 997–1006.
improve the implant’s in-vivo life by es in the composition resulted in inad- 16. A. Simchi and H. Pohl, Mater. Sci. and Eng. A, 359
reducing wear-induced osteolysis. In- equate mixing and unmelted Ti-6Al- (2003), pp. 119–128.
17. Félix A. España et al., Journal of Materials Sci-
dependently controllable two-powder 4V powder in the first few layers of the ence—Materials in Medicine (submitted December
feeders in LENS enable variation of transition region. Such microstructural 2007).
composition and porosity simultane- non-uniformity can be eliminated ei- 18. B. Vamsi Krishna, Susmita Bose, and Amit Bandyo-
padhyay, J. of Biomedical Research B: Applied Bioma-
ously in one operation to manufacture ther by increasing the laser energy in- terials (submitted April 2008).
such novel implant structures. Func- put or by using a finer alloy powder. 19. Weichang Xue et al., Acta Biomaterialia, 3 (2007),
tionally graded structures with a hard Gradient coatings with 86% Co-Cr- pp. 1007–1018.
20. B. Vamsi Krishna et al., Acta Biomaterialia (2007),
and wear-resistant Co-Cr-Mo alloy sur- Mo in the top surface showed ~184% doi:10.1016/j.actbio.2007.10.005.
face on one side and a porous Ti-6Al- increase in the surface hardness (com-
B. Vamsi Krishna, Weichang Xue, Susmita Bose,
4V alloy on the other side with a met- pared to 100% Ti-6Al-4V alloy) with and Amit Bandyopadhyay are with W.M. Keck Bio-
allurgically sound interface have been more than double the living cell densi- medical Materials Research Laboratory, School of
produced using LENS.20 These compo- ty observed on 100% Co-Cr-Mo alloy. Mechanical and Materials Engineering, Washing-
ton State University, Pullman, WA 99164-2920, USA.
sitionally graded structures consisted This demonstrates that the application Dr. Vamsi Krishna can be reached at vamsi23@ya-
of 100% Ti-6Al-4V alloy in the first six of LENS to fabricate novel porous and hoo.com.

48 www.tms.org/jom.html JOM • May 2008

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