Andani 2014

Accepted Manuscript
Metals for Bone Implants, Part 1: Powder Metallurgy and Implant Rendering
Mohsen Taheri Andani, Narges Shayesteh Moghaddam, Christoph Haberland,

David Dean, Michael J. Miller, Mohammad Elahinia
PII: S1742-7061(14)00272-4
DOI: http://dx.doi.org/10.1016/j.actbio.2014.06.025
Reference: ACTBIO 3282
To appear in: Acta Biomaterialia
Received Date: 17 February 2014

Revised Date: 8 May 2014
Accepted Date: 11 June 2014
Please cite this article as: Andani, M.T., Moghaddam, N.S., Haberland, C., Dean, D., Miller, M.J., Elahinia, M.,
Metals for Bone Implants, Part 1: Powder Metallurgy and Implant Rendering, Acta Biomaterialia (2014), doi: http://
dx.doi.org/10.1016/j.actbio.2014.06.025
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[Type text]
Metals for Bone Implants, Part 1: Powder Metallurgy and Implant Rendering
Mohsen Taheri Andani, Graduate Student1

Narges Shayesteh Moghaddam, Graduate Student 1
Christoph Haberland, Ph.D., Postdoctoral Research Associate1
(christoph.haberland@utoledo.edu) 1
David Dean, Ph.D., Associate Professor (tel: (614) 688-9044; fax: (614) 688-2195; e-mail:
David.Dean@osumc.edu)2
Michael J. Miller, M.D., Professor and Chair (tel: (614) 293-9885; fax: (614) 293-9024; e-mail:
Michael.Miller@osumc.edu)2
Mohammad Elahinia, Ph.D., Associate Professor (tel: (419) 530-8224; fax: (419) 530-8206; e-
mail: mohammad.elahinia@utoledo.edu)1*
Departments of:
1
Mechanical Industrial and Manufacturing Engineering, University of Toledo, 2801 W. Bancroft
St. MS 312, North Engineering 2045, Toledo, OH 43606 USA.
2
Plastic Surgery, The Ohio State University, 915 Olentangy River Road, Columbus, OH 43212
USA
*Communicating author
Running Head: New Metals for Bone Implants

Short Title: Mandibular Implants
Keywords: mandible, additive manufacturing, stress shielding, nitinol (NiTi), magnesium (Mg)
Abstract Words: (205)
Manuscript Words: (7284 with figures 6601 without figures)
Figures: 10, Tables: 2
For Submission to: Acta Biomaterialia
New Metals for Bone Implants Prepared for Submission to “Acta Biomaterialia”
Abstract
New metal alloys and metal fabrication strategies are likely to benefit future skeletal
implant strategies. These metals and fabrication strategies form the point of view of standard-of-
care implants for the mandible were looked. These implants are used as part of the treatment for
segmental resection due to oropharyngeal cancer, injury, or correction of deformity due to
pathology or congenital defect. The aim of this two part paper is to review the issues associated
with the failure of existing mandibular implants that are due to mismatched material properties.
Also potential directions for future research was studied. To mitigate these issues the use of low-
stiffness metallic alloys has been highlighted. To this end, development, processing and
biocompatibility of superelastic NiTi as well as resorbable Magnesium-based alloys were
discussed. Additionally, engineered porosity was reviewed as it can be an effective way of
matching the stiffness with the tissue surrounding an implant. These porosities and the overall
geometry of the implant can be optimized for strain transduction and with a tailored stiffness
profile. Rendering patient-specific, site-specific, morphology-specific, and function-specific
implants can now be achieved using these and other metals with bone-like material properties by
additive manufacturing. The biocompatibility of implants prepared from superelastic and
resorbable alloys was also reviewed.
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1. Introduction
This two-part paper intends to review the use of metals for regeneration of mandibular
functions through reconstructive surgeries that address cancer, other pathologies, trauma, or
congenital deformities. The American Cancer Society estimates that there were 41,380 new cases
of oropharyngeal cancer diagnosed in the US in 2013 [1]. It is known that gingivobuccal cancers
have early mandibular involvement for which the standard of care is resection. In many cases
resections leads to a segmental defect (i.e., a gap between two osteotomized parts). Similar, the
repair of mandibular fractures may involve a segmental defect. These are the most common
facial fracture, making up about 10% of civilian emergency room trauma. Whereas,
Craniomaxillofacial injuries make of 26% of battlefield injuries sustained in Operation Iraqi
Freedom/Operation Enduring Freedom (Afghanistan) [2].
For the past 25 years the field of regenerative medicine has been dominated by efforts at
tissue engineering. For most of this time the emphasis has been to regenerate or replace whole
organs with relatively simple constructs, assuming that the body would know how to remodel
them to its needs. The emphasis has also been to replace only what is needed with a properly
shaped, i.e., patient-specific, construct. The current clinical realization is that composite implants
that regenerate as much well-functioning tissue as can be reliably accomplished must often be
augmented with inert material components that will help bring about function, such as chewing
and speaking in the case of the mandible, as quickly as possible.
The clinical goal with mandibular implants is to provide a substrate for muscles and
loading, either during normal activities (e.g., chewing or speaking) or trauma (i.e., to protect the
contents of the oral cavity), that recreates the skeleton’s original stress-strain trajectories.
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Additive manufacturing (3D printing) has made it possible to design and render patient-specific
shapes that can appropriately translate strain through reconstructed anatomy [3, 4].
The available materials for 3D printing of craniofacial implants are, primarily, polymers,
ceramics, or metals. Most of the materials that have been vetted for 3D printing have
inappropriate strength and stiffness characteristics (i.e., too strong and stiff) for use as bone
implants [5-7]. While, an over-arching goal in choosing implant materials is to minimize or,
better yet, eliminate the modulus gradient between host tissues and the implant as well as to
recreate the patient’s previous stress-strain trajectories within the reconstructed mandible,
especially to regenerate the patient’s abilities to swallow, eat, breath, and speak. In order to
preserve the muscles of mastication, which are also crucial for moving the mandible during
speech, mandibular reconstructive surgery is usually attempted immediately following traumatic
injury to the mandible or segmental mandibular resection for cancer or other pathology.
Current standard of care involves stabilization with permanent titanium plates replacing
the bulwark of the resected mandible [8-10]. Because the gingiva (gums) do not integrate well
with titanium, it is common to transplant and affix fibular or iliac bone to these titanium plates
[11, 12]. This bone both integrates with the overlying gingiva and provides seating for titanium
dental implant posts [13]. Despite the loading of these implants during chewing [14, 15],
unfortunately the bone may be sufficiently stress-shielded by the titanium plates that it fails
during chewing. The choice to stress shield the transplanted bone is because the only available
metals are not able to smoothly transfer the strain created from chewing to the grafted bone.
In this paper the development, manufacture, and biocompatibility of superelastic and
resorbable metals with an emphasis on developing patient-specific implants that can transduce
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strain in a fashion more similar to bone and may be able to allow for a more stable design and
fabrication of implants to repair mandibular segmental defects were reviewed.
2. Modulus of the mandibular bone
Generally, 5 types of bone are in human body: long bones (femur, humerus and tibia), short
bones (carpals and tarsals), flat bones (scapula, sternum, cranium, os coxae, pelvis and ribs),
irregular bones (vertebrae, sacrum and mandible), and sesamoid bones (bones in tendons, e.g.,
patella, and pisiform). Each type of bones is made up of an outer shell of dense compact bone
(i.e., cortical bone) and an inner part which is a core of porous cellular, cancellous, spongy or
trabecular bone and/or bone marrow [16, 17]. The mechanical properties of the strong cortical
portion of a bone depend on its anatomic site and the local demands of weight bearing as well as
stress received from attached muscles, ligaments, and joint capsules. For instance, cylindrical
long bones that bear the highest loads and muscular forces usually have a thick and hard outer
surface of cortical bone, while short bones and irregular bones have a thinner outer layer [18].
In order to ensure an implant’s successful performance, it is helpful for it to have mechanical
properties as similar as possible to the tissue that surround, and will attach to, it. Of course the
shape of the implant’s attachment site is also important in recreating normal stress-strain
trajectories. Modulus of elasticity of an implant can be a very important mechanical property to
include in an implant’s mechanical design if one is to prevent stiffness mismatching—the other
being geometry (please see a discussion of the role of geometry in section 6 and in Part II of this
paper). There are various models and prediction methods for determining the stiffness of the
trabecular and cortical bone that will attach to an implant. In one approach, elastic properties of
bone are related to the bone density, which is measured by CT data such as dual energy X-ray
absorptiometry (DEXA) or quantitative computed tomography (QCT). In experimental studies,
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the type of end support during testing, specimen geometry, and anatomical sampling location
have also been shown to be important components of the simulation [18, 19].
Nagasao et al. divided the mandible into 42 sections (21 sections on bilateral sides) and each
section was further divided by 20 coronal planes. Young’s modulus of each of 840 subsections,
based on CT density of each subsection, has been calculated using the method of Kopperdhal et
al. [20]. The results are listed in Table 1. The range of modulus of cortical bone in the mandible
is 17.6-31.2 GPa, and the range for cancellous bone in the mandible is 1.5-4.5 GPa.
3. Modulus of surgically relevant metals
The range of Young’s moduli for the mandible, depending on the region, ranges from 17.6-31.2
GPa(Table 1[20]).The metals used for implants include stainless steel, cobalt alloys such as
cobalt-chromium, titanium alloys, tantalum and nickel titanium. These materials all have larger
moduli of elasticity than bone. The modulus of elasticity of various alloys is shown in Figure
1[21-23]. At 48 GPa, among the material listed in the table, superelastic alloy NiTi has one of the
lowest modulus. The other alloys of interest are magnesium-based. These alloys provide the
possibility of implant resorption and thus are candidates for immobilization hardware that will
resorb at a later date rather than require surgical removal. Magnesium as the base material has a
modulus of 45 GPa. However, if any of these metals are left in an implant site long enough, over
time this modulus difference leads to loosening of implants in areas of inappropriate stress
concentration and areas of bone resorption due to weak strain resulting from stress shielding. As
explained in this two-part paper, stress concentrations and shielding may be the major causes of
implant failure.
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4. Superelastic alloy NiTi
Shape memory alloys (SMAs) are distinguished from conventional metallic materials by
their ability to restore their shape after a large deformation, which can significantly exceed the
limits of elastic deformability of other materials. This shape memory effect (SME) was first
observed in 1932 in a Gold-Cadmium alloy as a thermally induced change in the crystal structure
[24, 25]. Nearly 20 years later Chang and Read identified the fundamental mechanisms in the
crystal lattice and attributed this phenomenon to a thermo-elastic behavior of the martensitic
phase[26]. In the following years SME was observed in more than 25 binary, ternary or
quaternary alloys and alloy systems [27]. Nickel-Titanium (NiTi) is the main alloy that has been
widely used [28]. SME in NiTi was observed for the first time by Buehler et al. at the U.S. Naval
Ordnance Laboratory (NOL, White Oak, Maryland) in the 1960s [29, 30]. Therefore, besides
NiTi or TiNi the term “nitinol” is commonly used to refer to this alloy.
Today, more than 90 % of all commercial shape memory applications are based on binary
NiTi or ternary NiTi-Cu and NiTi-Nb alloys [28]. This is despite the fact that both of NiTi’s
main elements, high purity Nickel and Titanium, are relatively expensive. Also manufacturing
processes for NiTi are challenging and expensive. The dominance of these alloys is due to the
excellent structural and functional properties of NiTi-based SMAs. In addition to a well-matched
modulus of elasticity for bone implants, the SME in NiTi allows for relatively large reversible
deformations of up to 8% and is also characterized by good functional stability [28, 31-33]. NiTi
also has good corrosion resistance and biocompatible properties, making this alloy an attractive
candidate for various medical applications such as surgical tools, stents or orthodontic wires [33-
36].
Page 7
The occurrence of the SME is due to the martensitic phase transformation. This solid
state crystallographic phase transformation is between a high temperature phase (β – phase,
austenite) and a low-temperature phase (α - phase, martensite). The transformation is
diffusionless and therefore local concentration of the chemical composition is not affected; only
the crystal structure changes. This change in crystal structure is driven by a shear process, which
can be described by a coordinated, cooperative movement of the atoms in the crystal lattice.
An important phenomenon for medical implants, pseudoelasticity or superelasticity,
results from this transformation, and is driven by an applied force. [37-41]. In contrast to the
thermally activated effects, in pseudoelasticity, no temperature change is required. An external
mechanical load is sufficient to induce this phase transformation. As shown in Figure 2, the
transformation 1 → 2 consists of transforming the austenite phase to detwinned and favored
oriented martensite variants. When the material is unloaded before having reached the yield
stress of the detwinned martensite where dislocation plasticity starts, the martensite transforms
back into austenite phase. Macroscopically this means undergoing and recovering a large level of
deformation and strain. As the schematic in Figure 2b shows, during loading and unloading the
material shows a hysteresis because of different stress levels for the actual transformation. In
addition to a favorable level of modulus of elasticity and large recoverable strains, this
hysteresis, corresponds well to the structural behavior of human bone under mechanical load
[33].
Ni-rich alloys which their stress-strain behavior of them is shown in Figure 2 are used for
pseudoelastic applications due to their low transformation temperatures. The phase
transformation temperatures of Ni-rich NiTi strongly depend on the Nickel-Titanium ratio of the
B2 matrix [42-44]. This dependence can be used to adjust the phase transformation temperatures
Page 8
by the nickel-titanium ratio. On the other hand, the effect of impurity related phases has to be
taken into account. During high temperature processing, the pick-up of impurities, such as
Carbon and/or Oxygen, can result in the formation of Ti-rich phases, since the B2 phase has a
low solubility for both elements [45]. Carbon forms carbides of type TiC [46, 47], while Oxygen
is dissolved in the Ti2Ni phase and forms a stable phase of type Ti4Ni2OX [45, 48]. In addition
to the degradation of functional and structural properties, the impurity pick-up during the
formation of these Ti-rich phases also results in a shift of the Nickel-Titanium balance. However,
that shift raises the Nickel content. In contrast to precipitation of Ni-rich phases, this causes a
decrease in transformation temperatures. Alloys can thus be produced, which show either a
thermal or pseudoelastic memory effect depending on the ambient temperature by considering
the aforementioned issues during manufacturing and processing of NiTi alloys.
5. Resorbable Mg-based alloys
While the earliest report of magnesium alloys as implant materials dates to 1878, it is
only recently—with the bulk of the publically reported research being done in the last 4-5 years--
that the topic of resorbable metals has been an area of significant investigation. The most
intriguing is to use these metals as safe, lightweight, initially strong but later resorptive, fixation
devices. However, this recent biomedical interest has only been in the research community.
Commercial translation of these alloys to clinical advances is limited by the lack of clear
applications, design methodology, and fabrication strategies for the envisioned medical devices.
It may be that none of the commercially available Mg alloys will prove useful for the preparation
of resorbable bone fixation hardware. However, several opportunities exist for designing bone
implant components and fixation devices from as yet untried resorbable metals and alloys, such
Page 9
as iron [49, 50] and zirconium [51-53] have been studied, the most intriguing of these metals is
Magnesium (Mg). This metal can be configured to form strong implant that can be tuned to
resorb following the expected bone wound healing process of 2-3 months. The healing process
can be tracked non-invasively via x-ray. If it is proceeding as expected, surgery to remove the
resorbable fixation device will be unnecessary reducing risk, discomfort, and cost for the patient.
If the bone wound is not healing at the expected pace, an intervention to place non-resorbing
fixation can be done.
There are many Mg alloys that have been shown to slow the corrosion (degradation) rate
in biomedical applications, especially bone. These alloy substances have often included rare
earth elements [54]. Other promising Mg alloys have included Sr (Mg-Sr degradation has been
shown to result in hydroxyapatite formation—which could assist integration with host bone) [55,
56]. Mg-Zn-Zr alloys have been shown to have high strength and have been considered for load-
bearing applications [57]. Advantageous degradation and strength properties can be safely (non-
toxic) obtained by inclusion of Zn [57, 58], e.g., Mg-Sr-Zn and Mg-Nd-Zn-Zr [59, 60], possibly
smoothing the modulus gradient in a composite implant [61]. Interestingly inclusion of Zn, i.e.,
Mg-Zn, strengthens the alloy but quickens its degradation in combination with Sr [62] while
slowing degradation dramatically in Mg-Zn versus pure Mg [63]. The in vitro degradation of
Mg-Zn-Al has also been studied [64]. Mg-Zn-Ca alloys have been investigated for bone fracture
fixation [65]. Mg2Ca is to be avoided when preparing Mg-Ca alloys, it can cause galvanic
corrosion [66, 67]. Hydroxyapatite has also been studied as a component in Mg alloys [68]. Rare
earth-containing alloys, such as Mg-Sc-Y, have also shown promise for use in bone fixation as
they actively form a “self-passivating” layer of oxide on the surface (i.e., a more stable oxide
than MgO), slowing the degradation rate enough to allow strong osteoblast (bone progenitor cell)
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attachment and proliferation [69, 70]. The co-implanting of Cr and O in Mg has been studied
[71]. Bulk metallic glass alloys, such as Ca-Mg-Zn show good degradation and material
properties, however the narrow range in which their high temperature formation occurs may
make it difficult to use additive manufacturing technologies [72-75].
6. Production of porous metallic implants
Over the years, porous materials have been used in surgical implants, as coatings on
prostheses for biological fixation; (as scaffolds to improve regeneration of tissue; and for
fabricating implants [76]. The concept of fabricating porous materials was first presented by
Sosnik in 1943 when he added mercury to the melt to make pores in aluminum [77]. Later, the
biomedical application of porous materials has been investigated by using porous metals for
osseointegration [78]. Over the years, a variety of fabrications methods have been developed
[79-82]. Porous metals are classified into closed-cell and open-cell. In closed-cell materials a
unit cell is enclosed by thin walls, while open-cell materials and foams are the result of
overlapping interconnected cells. The size, shape and location of cavities or pores depend on the
parameters of the fabrication process [83]. One of the benefits of porous structure as implants is
the possibility of bone ingrowth through the porous space. The other advantage of
porous structure is the reduction in the stiffness. This feature may be used to create a better
modulus match between an implant and the surrounding bone by introducing porosity in the
design. Summary of various fabrication methods for porous metals and properties of the resulting
pore distribution are shown in Table 2.
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7. Fabrication methods for porous NiTi
Fabrication of NiTi elements requires a considerable effort to account for the sensitive
structural and functional properties of this alloy. Usually, the initial step is the alloying
procedure. Some exceptions may exist for special powder metallurgical processing methods
where alloying and shaping are combined in one processing step. NiTi always is usually
produced by melting under vacuum due to the high reactivity of the melt. This usually requires
vacuum induction melting (VIM) or vacuum arc remelting (VAR) of elemental Nickel and
Titanium. Less financially viable methods include electron beam or plasma melting. Since cast
NiTi has inadequate structural properties and very low functional properties, usually multistage
thermal and thermo-mechanical treatments (solution annealing and/or homogenization, hot
forging, cold forming followed by recrystallization annealing, aging treatment) have to follow
the casting process. Shaping and the fabrication of finished NiTi components generally can be
done by subtractive methods, welding, forming, etc. In addition to challenges in machining NiTi
[84-87], conventional processing routes do not allow for the production of porous NiTi.
Using liquid phase processing for production of porous NiTi is restricted since the melting
point of NiTi is high (~1583 K). Due to high melting temperature and high density (6.45 g/cm³),
injecting a gas into a NiTi melt that is used for metallic foams (e.g. Aluminum foams) is
challenging [88]. There have only been two approaches for liquid phase melting procedures to
produce porous NiTi or NiTiCu. Sugiyama et al. describe a zone melting method for NiTi rods
under a Hydrogen/Helium atmosphere [89]. The hydrogen is initially dissolved in the melt and
then during directional solidification rejected which results in creating aligned and elongated
pores. Young et al. used pre-sintered SrF2 salt foams as space holders in a replica cast method.
Firstly, the alloy is molten under vacuum followed by applying gas pressure (Ar, 1 atm) to
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infiltrate the foam with liquid. After solidification and cooling down the space holder is removed
by ultra-sonicating in a solution of distilled water and 20 % HNO3. The results were porous
NiTiCu foams with about 60% porosity. The authors report on changes in transformation
temperatures due to presence of secondary phases (Oxygen stabilized Ti2 (Ni, Cu)). However,
they showed high deformation recovery in mechanical testing and very low stiffness (< 3GPa
during loading).
Powder metallurgical methods for producing porous NiTi are more common. Powder
metallurgy (PM) methods usually provide a near-net-shape product, which could significantly
simplify the manufacturing process. The main drawback is that due to the large surface area of
the powder particles and due to at least two additional high-temperatures processing steps
(powder production, PM process) NiTi components produced by PM usually contain high
contaminant levels [85]. For example, Schetky and Wu report typical Oxygen content is between
1500 and 3000 ppm [90]. As described before, high impurity levels may degrade structural and
functional properties of NiTi considerably. Nevertheless, the literature shows several established
PM routes as well as some promising PM approaches for the production of NiTi. In the
following sections several of these techniques based on either the mixture of elemental powders
(Ni and Ti) or pre-alloyed NiTi powder are discussed. When using a mixture/feedstock of
elemental powders a precisely controlled process (e.g., sintering temperature) is crucial.
Otherwise, due to different diffusion behavior and diffusion velocities, Ni or Ti-rich precipitates
may form in addition to NiTi. Also, some areas may consist of pure Nickel or Titanium [91, 92].
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7.1 Powder metallurgical fabrication methods for porous NiTi
7.1.1 Conventional Sintering
The simplest PM procedure is the conventional sintering of loose or compacted powders at a
temperature close to the melting point. Both pre-alloyed NiTi powder [93] as well as mixtures of
elemental powders have been used [94-97]. Instead of pure Titanium powder or in addition to
pure Titanium powder, also the use of TiH2 is described in the literature. Here, the hydride acts
as a blowing agent, which decomposes and releases hydrogen. The addition of TiH2 may
accelerate the reactive sintering process and may decrease oxidation of the Titanium. Also, TiH2
is less expensive than pure Titanium [98]. However, proper process control is essential when
using mixtures of elemental powders or TiH2. Li et al. [98, 99] and Zhu et al. [97] both observed
secondary phases and pure Nickel or Titanium in the resulting sintered product. Since in
conventional sintering there is a limitation in part geometry and pore size [88], this method
hardly offers potential for complex net-shape porous NiTi components. Also, conventional
sintering does not allow for an independent control of pore size and volume fraction, which are
determinants for the thermo-mechanical properties in porous NiTi. In particular, sintering
typically leads to relatively low porosities and small pores, which are affected by the initial
powder size. In addition, structural strength may often be reduced due to incomplete sintering of
the powders [100]. However, successful applications have been reported which use conventional
sintering or advanced sintering techniques such as spark plasma sintering (SPS, also known as
field-activated pressure-assisted synthesis, see Figure 3a)[101] for the production of dense NiTi
and porous NiTi, in particular [92, 101, 102]. In SPS, a feedstock consisting of either a mixture
of elemental powders [101] or pre-alloyed powder [102] is compacted, usually in a graphite or
steel die [101]. This pellet compact is then exposed to a high electric current density and the
Page 14
Joule heat results in activation of diffusion leading to densification of the powder followed by
homogenization to NiTi. The reaction is very quick and the temperature is relatively low, which
is beneficial in avoiding impurity pick-ups [102]. The secondary phases however may be present
in the resulting alloy [101]. In both, SPS and conventional sintering pore sizes, porosity, and
microstructure strongly depend on processing conditions and on the properties of the initial
powder. Porosities from nearly dense up to more than 60% are reported [94], but the pore sizes
are usually comparatively small ranging from 4 µm [103] to a not more than 100 µm (see Figure
3b[96]). To increase the pore size, Zhang and Li used temporary space holders [104-106]. A
mixture of elemental powders (average particle size 61 µm for Nickel and 50 µm for Titanium)
and ammonium acid carbonate powders (NH4HCO3, average particle size 250 µm, volume
fractions ranging from 10 to 30%) was the starting point. These mixtures were cold compacted
and then heated up to moderate temperatures (543 K) to remove the space-holders. Finally, these
green parts were sintered and highly porous NiTi was obtained with pore sizes up to 416 µm (see
Figure 3c[104]). Xiong et al. reported porosities up to 87% and pore sizes up to 500 µm [105]. It
is worth noting that such highly porous samples do not exhibit sufficient mechanical and
structural strength. There is also the possibility of processing graded porosity in sintering by
preparing a compacted powder batch of layers with different space-holder volume fractions.
Bansiddhi and Dunand recently introduced a novel sintering method for porous NiTi
[107, 108]. They developed a transient liquid phase sintering procedure combining the space-
holder method to control the porosity and a eutectic liquid brazing method of pre-alloyed NiTi
powders. Initially, NiTi powders (note: they also added pure Nickel powder to their mixture for
alloying Ni-rich NiTi) are mixed with NaCl space-holders and with Niobium as a transient liquid
phase sintering agent. This mixture is then cold pressed into a green pre-form and subsequently
Page 15
sintered. The temperature is slowly raised (heating rate: 10 K/min) to 1458 K which is above the
Nb-NiTi eutectic point. This slow temperature increase results in evaporation of NaCl (and
diffusion of the Nickel into NiTi powders) and, once the eutectic point is reached, in creating a
liquid. The transient NiTi-Nb liquid then infiltrates through capillary forces into small channels
between the partially sintered NiTi powders (where a Ni-rich composition has been previously
created by interdiffusion of Nickel into NiTi) but without filling the macro pores previously
generated by the space-holders. The microstructures of materials produced by this method are
quite inhomogeneous and show both secondary and eutectic phases. It is also important to note
that using pure Nickel in this method may result in the formation of Ni6Nb7 or Ni3Nb as well as
in insufficient bonding. The authors have therefore developed a methodology to separate the
different reactions (first: evaporation of NaCl and diffusion of Nickel to NiTi; second:
infiltration) by creating a layered feedstock [108].
The use of randomly distributed space-holders usually results in the formation of isolated,
equiaxed pores (this applies to other PM methods, as well). To create interconnected elongated
pore channels or networks in hot pressing of NiTi, Neurohr and Dunand developed a novel
method [109]. For this method, they used low-carbon steel wires woven into orthogonal meshes
as space-holders (see Figure 4a[109]). For tailoring the porosity they used different wire
diameters (356 µm and 711 µm) and different wire spacing (711 µm and 432 µm). These meshes
were initially pack-carburized in pure Carbon powders to supply Carbon to the wire surface so
that a TiC layer can form at the steel/NiTi interface which prevents interdiffusion between the
two phases during the later hot-pressing procedure. These meshes and pre-alloyed NiTi powders
were then poured into a die in an alternating manner and hot-pressed under vacuum. After
densification and cooling, the steel wires were removed electrochemically. Although this is a
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very innovative method for the production of interconnecting and accurate shaped pores, there
remains a TiC layer (~10 µm) on the surface of the channels which can affect the structural and
functional properties of NiTi.
7.1.2 Synthesis techniques
Synthesis of pure Nickel and Titanium to NiTi is an exothermic reaction. In synthesis
processes such as Explosive Shockwave Compression or Self Propagating High Temperature
Synthesis (SHS, also known as combustion synthesis) therefore elemental powders are used
[110]:
Ni + Ti → NiTi + 67 kJ/mol
Due to an initial reaction (i.e., thermal explosion) where the phase NiTi is produced from
elemental Nickel and elemental Titanium powders a local melt pool forms. Through a self-
sustaining reaction that propagates through the powder, the NiTi phase is finally formed in the
entire volume whereby capillary forces lead to pore formation. NiTi components produced this
way are usually highly porous (see Figure 5c) with interconnecting pores in the range of 250-360
µm [111]. However, SHS leads to uncontrollable and inhomogeneous pore size. Chemical
inhomogeneities are also difficult to avoid [100]. In particular undesirable intermetallic phases of
type Ti2Ni and Ni3Ti are usually formed [88, 112, 113]. This may be due to temperature
gradients during processing. Barrabés et al. contend that the maximum temperature in the
reaction zone can be lower, equal to or slightly higher than the melting point of NiTi [111].
Nevertheless, a porous NiTi implant (porosity: 65% ±10) for a proposed intervertebral fusion
device was produced by SHS. Biorthex (Montreal, Canada) has produced a commercial implant
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through this technique under the product names ActiporeTM PLFx and PNT (see Figure 5[114-
116]). Since 2001, this device has been implanted more than 1,000 times world-wide [117].
7.1.3 Hot Isostatic Pressing
Hot Isostatic Pressing (HIP) is usually used to produce fully dense materials from loose
powders. However, slight modifications in the procedure make HIP a very common method for
the manufacture of porous NiTi components. Here, the powder is usually encapsulated under
vacuum or under noble gas atmosphere in a container and sintered at high temperature.
Simultaneous application of isostatic pressure leads to a uniform density/porosity distribution in
the sintered part [118-120]. Lagoudas et al. also quote that HIP may be advantageous because of
decreased solid state diffusion time, HIP also offers the ability to control pore size and shape by
adjusting the process parameters [88]. During HIP, there generally is a pick-up of impurities
which can be limited by isolation from the atmosphere. In addition to the traditional HIP
procedure, capsule-free HIP has also been described. Here, the powder is cold pressed and then
heated up to moderate temperatures to create a pre-sintered, compacted part that does not require
a supporting capsule and which directly can be subjected to the HIP procedure [121, 122] . In
HIP, elemental powder mixtures or pre-alloyed NiTi powders are used. According to Lagoudas
et al., difficulties that may be encountered with the use of elemental powders to fabricate NiTi
via HIP are similar to those encountered using conventional sintering like the formation of
unwanted stable intermetallics [88]. They report the presence of secondary phases (NiTi2 and
Ni3Ti) as well as pure nickel and pure titanium in the resulting materials. In addition, they also
found deviations in the chemical composition in the NiTi phase. According to Köhl , due to
difficulties in control of the exothermic reaction and the Kirkendall effect, HIP of elemental
Page 18
powders may not be effective [123]. However, Lagoudas et al. describe the reaction, stating it
may be more stable and controllable compared to SHS [88].
For HIP of porous NiTi there are different approaches discussed in the literature. Several
authors describe a conventional HIP method with some modifications [88, 124-126]. A mixture
of elemental powders or pre-alloyed powders (both methods are described in literature) is loosely
packed into steel containers. After capping, the container is vacuum purged and then backfilled
with a noble gas (e.g. Argon). Then the temperature usually is raised at a low pressure for a short
period to initiate diffusion from Nickel and Titanium to the phase NiTi (differing parameters
have been reported) and to compact the powder. Next, the pressure is raised as solid-state
diffusion continues in the material. After release of pressure the material that is produced in this
way has a porosity of about 50% and an average pore size of approximately 20 µm [88]. It has
been reported that by slightly varying process conditions and using the expansion of the noble
gas (Argon) entrapped in the pores the pore size would be increased [88, 124]. As the
temperature exceeds the eutectic and peritectic temperatures of NiTi2 (1215 and 1257 K,
respectively) and approaches the melting point of Ni3Ti (1391 K), partial melting of the
diffusing powder mixture at sintering temperatures below the melting temperature of the phase
NiTi (1583 K) takes place. As this occurs, open pores containing high pressure Argon begin to
close and decrease in size, while trapping Argon in the diffusing medium. During subsequent
cooling and simultaneous pressure release, the compressed Argon can expand in the still soft
NiTi material. It is noted that the expansion can also be provoked after the actual HIP procedure
by a subsequent heating of the sample as described by Greiner et al. [124]. By applying the gas
expansion method, NiTi samples with about 40 % porosity and large, but closed pores of about
Page 19
500 µm can be produced [88]. This partial liquid phase method enhances the homogeneity of the
alloy but some Ni-rich phases are still observed in the material.
Another method for producing porous NiTi via HIP is described by Wu et al. [127], Zhang et
al. [128] and Bansiddhi and Dunont [100, 129]. In this method, which is very similar to the
approach described by Zhang, Xiong and Li [104-106] for conventional sintering, space-holders
are added to elemental powder mixtures [128, 130] or to pre-alloyed NiTi powder [100, 129].
Wu et al. [127] and Zhang et al. [104] use NH4HCO3 while Bansiddhi and Dumont use NaF
[100] and NaCl [129] as space-holders because of the thermodynamic stability in contact with
Nickel and Titanium. These methods have some significant differences. Wu et al. [127] and
Zhang et al. [104] cold compacted the feedstock to a perform and then heated it up under pure
Argon to remove the NH4HCO3 space-holders. These pre-treated compacts are then subsequently
subjected to a capsule-free HIP procedure. Depending on the ratio of Nickel, Titanium and the
space-holder, porosities of up to 48 % and pore sizes between 50 and 800 µm have been
observed [127]. In contrast to this method, Bansiddhi and Dumont [100, 129] remove the space-
holders after the HIP procedure. They assume that there is an advantage to doing this, because
removal of the space holder before HIP might increase the risk of pore collapse. In addition, the
use of NaF or NaCl space holders allows for an easy removal because they can be dissolved in
water. In their studies, Bansiddhi and Dumont [129] observe comparatively high mechanical and
structural characteristics for porous NiTi, which could be due to the comparatively low porosity
(~35 %) and small pore size (~160 µm).
It is clear that in HIP the different methods and mechanisms used to create porosity (space
holder and gas expansion) will result in different porosities but also in different pore formations,
pore morphologies and pore sizes (see Figure 6 b)[122] and c)[127]).
Page 20
7.1.4 Metal Injection Molding
Metal Injection Molding (MIM) seems to be very promising for the production of dense and
porous NiTi parts. While Guaxin et al. [131] use the conventional MIM process for the
production of porous NiTi from elemental powder, Bram et al. [132, 133] and Köhl et al. [134-
136] adopted the space-holder technique to create highly porous NiTi with large pore sizes and
good structural and functional properties by MIM from pre-alloyed powder (see Figure 7). This
procedure starts with creating a feedstock of NiTi powder, NaCl space-holders and a binder
system (amide wax and polyethylene wax) by means of mixing in a heated kneader. This
homogeneous mixture is then injected in a heated MIM tool. After removal and cooling a first
debinding step at elevated temperature (~ 420 K) is carried out to remove the binder system. In a
next step the space-holders are dissolved in distilled water and finally a combined second
debinding and sintering step under vacuum is carried out. Figure 8 shows samples taken at these
different process stages and a cross section of a sintered porous NiTi sample.
In contrast to the aforementioned methods, MIM is characterized by several distinct
advantages. MIM offers near-net-shape fabrication of complex parts, while the aforementioned
processes only allow for the production of simple geometries. With MIM part sizes from 2-50
mm can be created and parts of up to 1 kg have been processed [123]. In addition, MIM offers
high throughput and therefore, MIM is efficient for manufacture of higher quantities. Depending
on the type of space-holders, relatively large pores, defined porosities, and acceptable impurity
contents can be produced by this method. Additionally, Köhl et al. demonstrated promising
structural and functional properties in MIM-generated parts. Highly porous NiTi (porosity: 50%)
pronounces full pseudoelasticity of up to 6% under static compression load [135].
Page 21
8. Additive Manufacturing of NiTi
Recently, Additive Manufacturing (AM) has gained significant attraction and has been
applied to the production and scientific testing of NiTi implants [137-151]. Generally, Generally,
the term AM describes processes which are used to create physical parts directly from CAD data
by adding material in successive layers. For AM of metals these layers are usually provided in
powders and molten by a laser (note: other energy sources, e.g., electron beam, are available, too,
but so far for processing NiTi only laser-based systems have been used). The most common AM
processes for making parts from NiTi are powder-bed technologies such as Selective Laser
Sintering (SLS), Selective Laser Melting (SLM), Direct Metal Laser Sintering (DMLS), and
LaserCusing. Here, the powder material is deposited in layers of 20-100 µm thickness by a
blade, knife or a roller. Other less common techniques for processing NiTi are flow-based
processes, like Laser Engineered Net Shaping (LENS) and Direct Metal Deposition (DMD),
where a nozzle directly delivers the powder by into the laser focus. As shown in Figure 9, a 3D-
CAD model of the part has to be sliced in horizontal layers. Each layer contains specific
information about the part geometry and the scan trajectories for the laser. In an iterating
process, a powder layer of a thickness according to the thickness of the sliced CAD layers is
deposited; then, the laser beam locally melts the powder according to the geometry information
for the layer. After solidification, solid structures remain which are surrounded by loose powder.
Afterwards a new powder layer is deposited on top of the previous layer. This procedure is
repeated until the desired 3D part is produced. For processing NiTi, the entire process is usually
done in an enclosed chamber filled with Argon to minimize oxidation.
Page 22
While in principle it is possible to use elemental powder mixtures [137, 138, 152-154],
the majority of published results are from pre-alloyed NiTi powder [137-146, 148, 150, 151].
The challenges involved with using elemental powder mixtures are similar to those in the PM
processes. Shishkosky et al. performed numerous studies on SLS of elemental powders. In the
resulting parts, they found intermetallic phases as well as pure Nickel and pure Titanium. When
using pre-alloyed powders, they did not find these inhomogeneities [150]. Meier et al. [144] and
Haberland et al. [144-146, 155] showed that by using pre-alloyed powders, the additively
manufactured parts are homogeneous and show high strength and functional properties, which
are similar to the properties of conventionally processed NiTi. AM NiTi parts have shown to
have very low impurity content, which satisfies the requirements for medical devices (ASTM
F2063-05) [139, 155]. Another advantage of this fabrication method is the possibility of creating
engineered porosity based on a CAD design. This opens up the possibility of fabricating parts
with interconnected pores, variable pore sizes (morphologies) and complex composite
bone/implant interfacing scaffolds (see Figure 10a). This technique can also be used to create
tailored stiffness profiles. Finally, AM offers the possibility of producing patient-specific
implants from imaging data such as CT scans (see Figure 10b and c). To date, the use of these
parts in regenerative medicine has been primarily with in vitro cell culture or in animal models.
9. Conclusions
In this paper the development and manufacture of superelastic and resorbable metals for bone,
especially mandibular implants are reviewed. A summary of the conclusions follows:
1. The range of Young’s modulus of cortical bone and cancellous bone for the mandible are
17,600-31,200 MPa and 1,500-4,500 MPa, respectively. Since the typical metallic
Page 23
implants are usually made from materials with a higher modulus, stress concentration and
shielding occurs near the implant over the time, causing the device to fail.
2. Among the common materials, NiTi with elastic modulus of 48 GPa and Magnesium
with modulus of 45 GPa are attractive for various medical applications. Mg-based alloys
are resorbable, lightweight and have a low stiffness, and degradation rate. But due to lack
of a rigid design methodology and fabrication strategy, their application is limited to
some specific purposes like hydroxyapatite formation and bone fracture fixation.
Superelastic NiTi is an exciting candidate for medical devices because of a flexible
modulus of elasticity, good corrosion resistance, biocompatibility and the ability to
undergo large reversible deformations.
3. Fabrication of porous NiTi elements due to their sensitive properties is challenging. Since
the melting point of NiTi is high, primarily two techniques are used to produce porous
NiTi through liquid phase melting. These methods include high zone melting methods for
NiTi rods under a Hydrogen/Helium atmosphere and use pre-sintered SrF2 salt foams as
space holders in a replica cast method. The parts made through the later method show
high deformation recovery and very low stiffness, but due to the presence of oxygen the
transformation temperature changes. The most common ways for producing porous NiTi
parts are Powder Metallurgical methods. The simplest PM approach is conventional
sintering which is limited in part geometry and pore size. Moreover, this method is not a
good option for complex net-shape porous NiTi. In advanced sintering techniques like
spark plasma, high porosity (up to 60%) and relatively large pore size in the range of 4-
100 µm has been observed. But these methods have the same limitation in controlling the
pore size and porosity as conventional methods.
Page 24
4. To control porosity in sintering, Bansiddhi and Dunand used a space-holder method.
However, the microstructures of fabricated materials were quite inhomogeneous and
showed both secondary and eutectic phases. In addition, Neurohr and Dunand used low
carbon steel wires as space-holder and porous NiTi with accurate and interconnecting
shaper pores were fabricated.
5. Self-Propagating High Temperature Synthesis (SHS) is a commercial manufacturing
technique for porous NiTi. Due to high induced capillary forces that occur during the
process, NiTi with high porosity and the pore size in the range of 250-360 µm can be
rendered. Uncontrollable and inhomogeneous pore size are the limitations of this method.
6. Another existing approach is Hot Isostatic Pressing (HIP). This method offers the ability
to control pore size and pore morphologies by using different mechanisms. The
challenging issue in this technique is the formation of unwanted stable intermetallic
similar to conventional sintering.
7. The major limitation of the aforementioned processes is that they can only be used to
produce simple geometries. Metal Injection Molding as a promising way for fabrication
of porous NiTi can overcome this problem. In this method, the near-net-shape fabrication
of complex parts with part size of 2-50 mm and acceptable impurity contents have been
fabricated. Another approach which has recently gained much attention is Additive
Manufacturing. In this method, the part is manufactured from an arbitrary CAD design
which allows the fabrication of parts with variable pore sizes and pore morphologies.
Also, additive manufacturing can be used to facilitate the production of patient-specific
implants based on CT scan data.
8.
Page 25
Acknowledgements:
The authors acknowledge funding by the US State of Ohio Department of Development through
grant WP10-010 (Nitinol Commercialization Accelerator). This paper has been substantially
improved by the comments of three anonymous reviewers.
References:
Page 26
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Tables
Page 34
Table 1.Young's Moduli (MPa) of Mandible [20]

Mandible Cortical Bone Cancellous bone
Symphysis 18900-22300 2340-3600

Parasymphysis 17600-23500 1500-2580
Angle 21300-25670 2500-4500
Ramus 20780-28700 2800-3500
Condyle 21900-26400 1800-2600
Coronoid 25600-31200 2640-3320
Table 2.Summary of various fabrication methods that would be useful for porous metals implants
[83]
Closed Cell Open-cell
Graded Pore Random Pore Non-homogenous Homogenous Functionally graded

Distribution Distribution
Plasma spraying Gas injection Sintered metal Orderly oriented Rapid prototyping
into the metal powders wire mesh
melt
Decomposition Sintered metal fibers Vapor deposition Electro discharge
of foaming compaction
agents
Space holder method Ferromagnetic
fiber array
Replication Rapid
prototyping
Combustion synthesis
Plasma spraying
Figure Captions
Figure 1.Modulus of elasticity of biomedical alloys
Page 35
Figure2. (a) Schematic of superelasticity (pseudoelasticity): stress-strain plot; (b) stress-strain-

temperature plot.
Figure 3.(a) Schematic of the Spark Plasma Sintering set-up(This figure is reprinted from
[101]);(b) Micrograph showing porous NiTi produced by conventional sintering(This figure is
reprinted from [96]) and (c) by sintering using space holders(This figure is reprinted from [104]).
Figure4. SEM micrographs (a) of a steel mesh space-holder, (b) of a porous NiTi scaffold
produced by hot pressing using these –space-holders (c) shows the pores at higher
magnification(This figure is reprinted from [109]).
Figure5. Porous NiTi interbody fusion device ActiporeTM produced by SHS: (a, b)
Photography, (c) SEM micrograph
[(a), (b), and (c) are reprinted form [114], [115],and [116] respectively].
Figure 6.(a) Schematic of HIP for porous NiTi using the gas expansion method(This figure is
reprinted from [124]), (b) SEM of a porous NiTi sample produced with gas expansion(This
figure is reprinted from [122]),(c) SEM of a porous NiTi sample produced with space holders
(This figure is reprinted from [127]).
Figure7. Schematic of MIM for net-shape porous NiTi using space-holders(This figure is
reprinted from [136]).
Figure 8.(a)Samples at different stages in processing porous NiTi via MIM using space-holders
(This figure is reprinted from [136]) (b)Porous NiTi produced via MIM using space-holders
(This figure is reprinted from [135]).
Page 36
Figure 3.Schematic showing the principle of powder bed-based Additive Manufacturing of a

complex NiTi scaffolds.
Figure 4. a) Complex NiTi implants and scaffolds produced by AM (This figure is reprinted from
[156]); b) patient-individual porous NiTi dental root implant produced by AM (note: the jaw
segments are also produced by AM but from 316L)( This figure is reprinted from [157]), patient-
individual mandibular implant produced by AM (material: 316L)( This figure is reprinted from
[158]).
Figure 1:
Page 37
Rhenium (Re) 470

CoCr (Cast) 240
AISI 316L 210
CP Ta 200
Tantalum (Ta) 186
Hafnium (Hf) 138
Ti-6Al-4V 112
Ti-29Nb-13Ta-2Sn 110
Ti-29Nb-13Ta-7.1Zr 110
Niobium (Nb) 108
Ti-29Nb-13Ta-4.5Zr 100
Ti-29Nb-13Ta-4.6Sn 91
Ti-29Nb-13Ta-6Sn 85
Ti-13Nb-13Zr 80
Ti-29Nb-13Ta-4Mo 80
Ti-29Nb-13Ta-4.6Zr(aged) 77
Ti-12Mo-6Zr-2Fe 74
Ti-15Mo-5Zr-3Al (ST) aged 74
Ti-16Nb-13Ta-4Mo 66
CP Ti 65
Ti-5Al-1.5B 62
Ti-6Al-7Nb 55
Dense NiTi 48
Magnesium 45
0 50 100 150 200 250 300 350 400 450 500
E(Gpa)
Page 38
Figure 2
Page 39
Figure 3
Page 40
Figure 4
Page 41
Figure 5
Page 42
Figure 6
Figure 7
Page 43
Page 44
Figure 8
Page 45
Figure 9
Page 46
Figure 10
Page 47
Stress Shielding and Using Low Stiffness
Material Ti6Al4V
Stress Concentration
Implant Failure Mg-Based
Mechanisms Corrosion and Optimized Geometry Safe
Alloys
Toxicity Risk (Part II) Lightweight
NiTi Resorptive
Mandible Implants and Infection (Part II)
Clinical Failure (Part II) Shape Memory Behavior
Superelasticity Behavior
Biocompatibility (Part II)
Engineered Porosity Fabrication Methods
to Tailor Stiffness (Powder Metallurgy) Conventional Sintering
Synthesis Techniques
Hot Isostatic Pressing
Bone Ingrowth (Part II) Metal Injection Molding
Biocompatibility (Part II)
Additive Manufacturing Patient-Specific, Site-Specific,
and Function-Specific Implants

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Accepted Manuscript

Mohsen Taheri Andani, Narges Shayesteh Moghaddam, Christoph Haberland,

To appear in: Acta Biomaterialia

Received Date: 17 February 2014

Mohsen Taheri Andani, Graduate Student1

Running Head: New Metals for Bone Implants

segmental resection due to oropharyngeal cancer, injury, or correction of deformity due to

biocompatibility of superelastic NiTi as well as resorbable Magnesium-based alloys were

discussed. Additionally, engineered porosity was reviewed as it can be an effective way of

profile. Rendering patient-specific, site-specific, morphology-specific, and function-specific

additive manufacturing. The biocompatibility of implants prepared from superelastic and

resorbable alloys was also reviewed.

Craniomaxillofacial injuries make of 26% of battlefield injuries sustained in Operation Iraqi

Freedom/Operation Enduring Freedom (Afghanistan) [2].

and speaking in the case of the mandible, as quickly as possible.

speech, mandibular reconstructive surgery is usually attempted immediately following traumatic

In this paper the development, manufacture, and biocompatibility of superelastic and

fabrication of implants to repair mandibular segmental defects were reviewed.

2. Modulus of the mandibular bone

In order to ensure an implant’s successful performance, it is helpful for it to have mechanical

trajectories. Modulus of elasticity of an implant can be a very important mechanical property to

include in an implant’s mechanical design if one is to prevent stiffness mismatching—the other

absorptiometry (DEXA) or quantitative computed tomography (QCT). In experimental studies,

3. Modulus of surgically relevant metals

4. Superelastic alloy NiTi

excellent structural and functional properties of NiTi-based SMAs. In addition to a well-matched

state crystallographic phase transformation is between a high temperature phase (β – phase,

austenite) and a low-temperature phase (α - phase, martensite). The transformation is

An important phenomenon for medical implants, pseudoelasticity or superelasticity,

thermally activated effects, in pseudoelasticity, no temperature change is required. An external

transformation 1 → 2 consists of transforming the austenite phase to detwinned and favored

pseudoelastic applications due to their low transformation temperatures. The phase

thermal or pseudoelastic memory effect depending on the ambient temperature by considering

the aforementioned issues during manufacturing and processing of NiTi alloys.

5. Resorbable Mg-based alloys

fixation can be done.

make it difficult to use additive manufacturing technologies [72-75].

6. Production of porous metallic implants

pore distribution are shown in Table 2.

7. Fabrication methods for porous NiTi

thermal and thermo-mechanical treatments (solution annealing and/or homogenization, hot

(powder production, PM process) NiTi components produced by PM usually contain high

elemental powders a precisely controlled process (e.g., sintering temperature) is crucial.

7.1 Powder metallurgical fabrication methods for porous NiTi

7.1.1 Conventional Sintering

The simplest PM procedure is the conventional sintering of loose or compacted powders at a

determinants for the thermo-mechanical properties in porous NiTi. In particular, sintering

of elemental powders [101] or pre-alloyed powder [102] is compacted, usually in a graphite or

infiltration) by creating a layered feedstock [108].

functional properties of NiTi.

7.1.2 Synthesis techniques

Synthesis of pure Nickel and Titanium to NiTi is an exothermic reaction. In synthesis

processes such as Explosive Shockwave Compression or Self Propagating High Temperature

7.1.3 Hot Isostatic Pressing

Simultaneous application of isostatic pressure leads to a uniform density/porosity distribution in

may be more stable and controllable compared to SHS [88].

(~35 %) and small pore size (~160 µm).

7.1.4 Metal Injection Molding

In contrast to the aforementioned methods, MIM is characterized by several distinct

pronounces full pseudoelasticity of up to 6% under static compression load [135].

8. Additive Manufacturing of NiTi

LaserCusing. Here, the powder material is deposited in layers of 20-100 µm thickness by a

done in an enclosed chamber filled with Argon to minimize oxidation.