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Biomaterials for hip implants - Important considerations relating to the

choice of materials

Article  in  Bio-Algorithms and Med-Systems · October 2017

DOI: 10.1515/bams-2017-0017

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 Bio-Algorithms and Med-Systems 2017; 13(3): 133–145

Review

Mieczysław Choroszyński, Mieczysław Rorbert Choroszyński and Stanisław Jan Skrzypek*

Biomaterials for hip implants – important

considerations relating to the choice of materials
https://doi.org/10.1515/bams-2017-0017 during use. All together they contribute to the wear, i.e.
Received July 28, 2017; accepted September 6, 2017 loss of weight, strength or volume of hip components. Wear
rates of ultrahigh molecular weight polyethylene mated
Abstract: This article is a review of important material
against Ti-6Al-4V are significantly greater than the ones
requirements for hip biomaterials including their response
for Co-Cr-Mo alloys. Therefore, thermochemical surface
to the body environment (biocompatibility), mechanical
treatments like diffusion ion nitriding should be applied
properties, wear resistance, fretting corrosion and avail-
to increase the resistance of titanium alloys to wear. Aus-
ability as well as the price. The application of proper bio-
tenitic stainless steels are also used for temporary applica-
materials for hip implants is one of the major focal points
tions, but they have lower resistance to pitting corrosion
in this article. Background information is also provided on
than titanium and cobalt alloys. The purpose of the paper
metals used in other prosthetic devices and implant com-
is to introduce a group of metallic materials, which is often
ponents. Titanium and its alloys, cobalt base alloys and
chosen for surgical hip implants. Conclusions of the paper
stainless steels (bio-steels) are used for load-bearing hip
refer to information which support important medical and
implants. These three groups of metallic materials will be
patient decisions on hip implants. Also, the development
introduced and discussed in detail. Metals and their alloys
of biomaterials, their treatments, properties, surface lay-
are crystalline materials since their properties depend on
ers and coatings are considered. All these features develop
the crystal lattice, chemical and phase compositions, grain
over time and need synergy and experience in the progress
size, lattice defects, crystalline texture and residual micro-
of the biomedical, mechanical and materials science.
and macro-stresses. All these features of biomaterials are
formed during technological manufacturing, such as met- Keywords: bio-steels; cobalt base alloys; desorption;
allurgical process, solidification, plastic deformation (roll- high biocompatible titanium alloys; microstructure and
ing and forging), machining, heat treatment and coating. mechanical properties; nickel, vanadium and aluminium
All these technological processes work in optimal condi- free alloys; osteointegration; stainless steels; toxicity.
tions in order to achieve the optimal microstructure and
mechanical, chemical and biological properties. Amongst
the above-mentioned particular properties of biomaterials, Introduction
fretting is a major concern as regards hip implants at the
femoral head and neck taper interface. Additional impor- The first hip joint replacement took place in 1926 in the
tant mechanisms of interaction between the implant and USA. Hip joint replacement is a major achievement
the human body must be taken into account, i.e. diffusion in orthopaedic surgery in the 20th century. Scientific
stream of foreign particles and atoms from the implant to research and experiments with a large number of human
body fluids, to the tissue and to the bone. These foreign body part implants are carried out. Medicine, mechani-
particles and atoms are released from the implant to the cal engineering, chemistry, biology, physics and material
body fluid, to the tissue and to the bone as wear product science have created particular divisions and branches
intended to investigate implants.
The synergy of medicine, biochemistry, biophysics,
*Corresponding author: Stanisław Jan Skrzypek, AGH-University of mechanical engineering, materials science and informat-
Science and Technology, Krakow, Poland, ics succeeds in development of real progress in ortho-
E-mail: [email protected] paedic surgery of hip joint implants. Recently, several
Mieczysław Choroszyński: Research and Development at Scientific
millions of hip joint replacements are made per year in the
Metal Treatment, Roselle, USA; and AGH-University of Science and
Technology, Krakow, Poland
USA. Similar progress takes place in many other countries.
Mieczysław Rorbert Choroszyński: Medical University of Silesia, Among others, the quality of the materials used and the
Katowice, Poland material science, in general, are involved in achievements

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134      Choroszyński et al.: Biomaterials for hip implants

in this interdisciplinary field. Therefore, this scientific Artificial bearing-hip implant

field with respect to hip joint implants is discussed and
considered in this article. Metallic shell (with bioactive Socket (polyethylene linear)
porous coating)
Most parts of hip joint implants are made of metal- Artificial neck
lic materials due to heavy and cyclic load bearing. Addi- Acetabulum bone (Sensitive to fracture)

tionally, they work in a bioactive environment. Titanium

Natural bearing
alloys are the most advanced materials in this type
of application; however, Co-Cr-Mo alloys and austen- Bioactive porous coating

itic stainless steels as bio-steels mated with appropri- Femoral head

ate metallic alloys, ceramics and polymers are the main Femoral stem
Natural neck
materials of hip implant components. Femoral heads and (sensitive to fracture)
sockets (cups) can also be made from advanced ceramic
materials. These statements are based on experience and Femoral bone
scientific biomedical investigations [1–10]. Additionally,
ultrahigh molecular weight polyethylene (UHMWPE), Figure 1: Artificial and natural hip (bearing) – typical components
in a total hip replacement implant – a typical hip prosthesis with
high-density cross linking polyethylene and polieteroeter-
a combination of metallic and plastic components consists of the
oketon are applied to produce the circular bearing. femoral stem, a femoral head and polymeric socket.
Metallic alloys are crystalline materials since their
properties strongly depend on the type of the crystal lattice.
The specific space atomic arrangement defines the crystal chemical and mechanical contacts of foreign material with
lattice, which in turn relates to the particular properties the bone, body fluids and tissues are most important char-
and their anisotropy. The chemical and phase composition acteristics of the implant, although the interaction between
of an alloy as the main characteristic has a major influence mechanical parts of a complex and modular implant is an
on the crystal lattice, grain size, lattice defects and crystal- additional serious area of scientific investigations. The
line texture. The microstructure revealed with microscopic components of modular implants (Figure 1) are exposed to
investigation provides information about the shape and degradation processes as fatigue loading, contact fatigue,
size of grains and precipitations, which is the third impor- corrosion, friction, abrasion and fretting. The abrasion and
tant characteristic of biomaterials. All these properties of fretting basically come from friction – unfortunately, they
biomaterials are formed during technological operations produce particles and debris on micro-, nano- and atomic
of production like the metallurgical process, solidification, scale. Therefore, the important interaction between parti-
sintering, metal forming (rolling and forging), machining, cles and debris with tissue, biological fluids and the bone
heat treatment and coating deposition. must be considered and taken into account [12].
All these technological processes are optimized in Modular designs of the hip implant, where the stem and
order to achieve the optimal structure and microstruc- the ball (Figure 1) are made of two different materials, are
ture coupled with the expected mechanical, chemical and common in practical applications. Modular orthopaedic hip
biological properties. The metallic components usually implants are widely used in total hip arthroplasty due to their
undergo additional surface treatments including coating clinical flexibility. Another example of a common practical
and alloyed surface layers deposition. solution can be as follows: the ball is made of either highly
Recently, titanium alloys are most often used in bio- polished Co-28Cr-6Mo alloy or ceramic sinters [e.g. alloyed
material applications due to an excellent combination of alumina (Al2O3) with zirconia (ZrO2)], whereas stem is made
properties. The titanium alloys are characterized by good of Co-based alloy [7, 8, 13–17]. Unfortunately, the modular
mechanical properties, low density, an acceptable tissue tol- type of hip prosthesis has revealed fretting corrosion and
erance, high strength to weight ratio, outstanding resistance related problems, particularly at the taper interfaces. Also,
to corrosion by body fluids, high biocompatibility, being a modular connection of the hip stem and head (Figure 1)
nonmagnetic and the capacity for joining with bone, i.e. oste- made of different materials is susceptible to galvanic cor-
ointegration [1, 4, 11]. Amongst others, it is important that rosion. Corrosion at the femoral stem/head taper interface
titanium is a material that will not introduce fibrous tissue may result from fretting due to micro motion, crevice at the
barriers in contact with a healthy bone. Another advantage taper mismatch and galvanic coupling of dissimilar materi-
of titanium is the fact that the fatigue properties of the load als or a combination of these three components.
bearing device are not reduced through contact with body Titanium alloys have a tendency to stick. All tita-
fluids containing aggressive chlorine ions. The biological, nium alloys have poor friction and abrasive properties.

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 Choroszyński et al.: Biomaterials for hip implants      135

Therefore, sliding contact of these alloys should be biomaterials will not introduce fibrous tissue barriers
avoided without modification of the surface layer by ther- during contact with healthy bone. This permits the bone
mochemical diffusion treatment (nitriding and/or car- to grow closer to the surface of the implant and to fill in
bonitriding) [18, 19]. However, the effective case (and the grooves or pores that have been deliberately introduced
total case) must be thick enough to be able to support the to a surface according to the Wolf law of bone growth to
case layer. Also, the case layer should have a proper gra- enable the device to become more firmly embedded.
dient-like distribution of microstructure, residual stress
and micro hardness versus thickness to avoid the stress
threshold or tension notch.
Wear rates for UHMWPE mated against the ­Ti-6Al-4V
General requirements for orthopedic
alloy are significantly higher than that for Co-Cr-Mo alloys implants
[6, 11]. Cobalt base alloys such as Co-Cr-Mo are the most
commonly used metals for the current metal on polymer Artificial solutions for human body disabilities must be
(UHMWPE) joint as friction couple in larger loaded bear- based on the mechanical design and actually available
ings of hip implant components for heavier patients. materials, which meet special requirements. These are
Femoral components are also made from Co-Ni-Cr-Mo mechanical, biological and chemical requirements that
alloys. Important reports on cobalt alloys have recently must be fulfilled for them to be used for the human body
been provided. It was about the easy diffusion of Co ions in line with the principles of medicine describing the
from hip implants to body fluids. In this way, concen- particular features of biomaterials. The above review of
tration of cobalt in blood can reach a higher level than the literature reveals complex issues, which are related
normal [20]. Although a majority of chemical elements of with medical, mechanical and material problems in hip
applied materials are building components of the human implants. Biomaterials used for hip prostheses should
body, it is usually harmful if their concentrations in some exhibit the following properties [6, 7, 9, 10, 13, 21]:
tissues, bone or in body liquids are over a natural level. 1. High biocompatibility (nontoxic and non-carcino-
The higher wear rates of UHMWPE associated with its genic, chemically stable and corrosion resistant);
counterpart made of titanium alloy are related to the 2. Nonmagnetic;
mechanical instability of the metal oxide layer under 3. The surface femoral stem should be bioactive in terms
high loading. Mechanical stress and chemical activity of osteointegration;
cause micromechanical and chemical mechanisms of 4. Adequate mechanical properties (Young modulus,
wear out called fretting corrosion. The fretting corrosion yield strength, tensile strength, ductility, hardness,
damage or mechanical fatigue is a major cause for failure toughness, fatigue strength and abrasive wear);
of orthopaedic implants. Fretting can mechanically 5. The femoral stem should be able to endure large and
damage the passive layer and generally surface layers variable stresses in the human body environment
of all metals. The Ti-6Al-4V and other similar alloys are relating to a large number of stress cycles, i.e. fatigue
used for hip implants in the annealed state. These alloys (e.g. during 10  years, assuming that the distance of
in the annealed condition are relatively soft and have 10 km in a day yields about 35 × 106 mechanical cycles,
low strength, and the substrates of these alloys are not i.e. steps) with additional stress corrosion, stress-
able to support the passive oxide layer exposed to heavy enhanced diffusion and even stress-induced phase
loading of working joints during use. Under a heavy load, transformation;
the oxide layer collapses (cracks) and produces a flux 6. Surface layer with gradient-like modulus of elasticity,
of particles. Normal stresses usually are high enough to i.e. with gradient-like porous distribution in surface
break down the surface passive layer causing oxide dis- layer;
ruption. The passive oxide surface layer on femoral heads 7. The surface of implants should be free of imperfec-
made of the titanium alloy results in an excessive wear tion, such as tool marks, scratches, nicks, cracks,
of the couple metal-UHMWPE socket [7]. On the other cavities, burrs and other defects;
hand, relatively soft alloy due to annealed microstructure 8. Surface texture as surface quality factor and surface
with lower internal stored energy is required because of geometry classification may vary from very smooth
stable bioactivity and corrosion resistance due to lower for bearings to rough for the femoral stem and socket.
internal stored energy. The bioactive surface of applied All this depends on the design, material, application
alloys for orthopaedic applications is very important for and the area involved in the metallic implant (e.g. the
achieving improved biocompatibility. It is important that fatigue crack initiation is significantly lowered when

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136      Choroszyński et al.: Biomaterials for hip implants

the surface is highly polished, whereas a rough sur- The resistance to fatigue crack nucleation depends on
face is demanded for better osteointegration); stress, microstructure and modulus of elasticity accord-
9. Well-balanced chemistry and proper metallurgical ing to the Paris law and Irvin and Weibull considerations
conditions of the alloy, i.e. proper chemical, phase [22, 23]. Fatigue cracks usually nucleate at the surface of
and microstructure composition, absence of segrega- the stressed metal, where the stresses are at a maximum
tion, nonmetallic inclusions and martensitic phase; taking into account surface residual stresses and the prin-
10. Availability, with reasonable balance between qual- ciple of superposition of any existing stress component.
ity, durability and price. In contact loading, the Hertz and Bielajew point with the
maximum reduced stress must be taken into account. Any
design or manufacturing defects and tensile surfaces with
Mechanical and materials require- residual stresses encourage nucleation and development

ments for orthopedic implants of fatigue cracks. The fatigue resistance of the material
can be expressed as the crack growth rate (da/dN) related
to applied stress, strength (s, K) and Young modulus (E) of
One of the goals in the development of new materials
the material [23]:
for hip implants was and still is an optimal ratio of the
elasticity modulus of metallic, ceramic and polymer parts da K
3.6

= C ∆K m = C a   (2)
and the bone. The modulus is an important concern in dN
E 
the orthopaedic application of biomaterials in terms of
the mechanical interaction between the implant and the
where
bone. The stiffness of the material can be described by
da/dN is the crack growth rate [mm/cycle]
Young’s modulus of elasticity (E). The ratio of stress (s)
C, Ca and m are the experimental constants
to strain (e) in the elastic deformation region is known as
ΔK = Δσ is the stress intensity factor during fatigue
the modulus of elasticity (E), or Young’s modulus. Young’s
factor
modulus is the tangent of slope angle of the σ = Ee strain
line function in the elastic region of the tensile test. The
where sharp crack occurs, the existence of a critical stress
constant of the proportion between the stress and strain
for rapid crack propagation is given by the relation
in the linear elastic region during tension is known as
Young’s modulus and defined as σ crict = E γ / πa (3)

Modulus of elasticity E = σ x / εx , where σcrit is the critical tensile stress

σ x = E εx ( here E as stiffness),  εx = σ x / E and E is Young’s modulus
εy = − νσ x / E (here 1 / E is susceptibility) (1) γ is the energy per unit area of new surfaces

a is the crack length for a surface crack and 2a = for an
The modulus of elasticity (E) is essentially a measure internal crack
of the material stiffness and is determined from the tensile
test or by the elastic internal dumping method (internal The stress from the applied loading must be lower than
friction) and by ultrasonic wave velocity measurements. the tensile strength of the material (Table 1). If the tensile

Table 1: Young modulus and mechanical properties of the bone and selected biomaterials.

Properties/material   Young’s  Poisson’s  Tensile ultimate  Tensile yield  Re/Rm  Bending

modulus E, ratio strength Rm, MPa strength Re, strength Rg,
GPa MPa MPa

Ultrahigh molecular weight polyethylene  55–170  0.42  >30  >20  –  –

(UHMWPE)
Bone cement   3.8  0.4  60  55  0.9  –
Compact bone   30  –  120  –  –  160
Ti CP Grade 4/annealed   105  0.37  560–880  380–520  0.7  340
Ti-6Al-4V/annealed   115  0.41  >890  >730  0.9  650
Cobalt alloys (Co-28Cr-6Mo)/annealed   230  0.36  >600  >500  0.6  –
Bio-steels (see Chap. austenitic steels)   210  0.29  480–900  180–600  0.6  250

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 Choroszyński et al.: Biomaterials for hip implants      137

strength of the material increases, the resistance to fatigue Rm, yield strength (R0.2), bending strength (Rb), torsion
also increases by the crack growth rate decrease [Eq. (2)]. strength, toughness and fatigue strength of the alloys con-
If Young’s modulus is larger, the crack growth rate is sidered should be also measured and analyzed (Table 1).
smaller and the critical stress to develop crack must be Mechanical properties depend on the microstruc-
larger [Eq. (3)]. ture which is characterized by grain size, grain crystal-
Reciprocal relation appears when there are differ- lographic orientation, crystal lattice defect density and
ences in an elastic module of the bone and the implant. phase composition. The last one is formed by phase trans-
Significant differences in the elastic moduli of the bone formation due to heat, thermochemical and thermome-
and the implant may lead to stress concentrations at their chanical treatments. Metal forming, i.e. cold and/or heat
interface, i.e. the stress threshold. An insufficient load plastic deformation, are important technological opera-
transfer from the artificial implant to the adjacent natural tions which influence lattice defects, grain size and their
bone may result in bone desorption and loss of the bone- orientation. Segregation of alloying elements can result in
implant joint, and finally, the whole hip implant can be the formation of non-uniform phases and microstructure
rejected. The low modulus of alloys reduces the mismatch composition with different crystallographic structures,
between the modulus of the implant and that of the bone, lowered corrosion resistance and fatigue strength and
which in turn reduces the so-called “stress shielding increased residual stresses and pitting corrosion. Agglom-
phenomenon”, which can be responsible for potentially eration or large amounts of other phases can reduce the
damaging resorption of bone on the inner surface of the fatigue life of implants. Segregation of non-uniform clus-
natural femur. Stress shielding is related to the difference ters acts as stress threshold in the microstructure. An alloy
in flexibility/susceptibility or stiffness between natural with segregated alloying elements is sensitive to nuclea-
bone and the implant alloy. The lower modulus of tita- tion of fatigue cracks. The fatigue or stress corrosion
nium alloys is a positive factor in reducing bone resorp- damage and abrasive wear are the major causes for failure
tion. However, the modulus of elasticity should not be too of orthopaedic implants. The fatigue strength yield point
low. An implant made from alloy with the too low Young’s ratio of applied biomaterials is small and ranges between
modulus of elasticity will have low resistance to nuclea- 0.3 and 0.7 with additional large safety coefficient which
tion of fatigue cracks and larger cracking velocity [Eq. makes the calculations of mechanical strength and total
(3)]. From this point of view the modulus of elasticity (E) reduced stress rather complex and difficult.
should be in the optimum range owing to the selection of
proper materials and/or proper production technology.
Recent attempts to minimize the modulus of elasticity
and improve biocompatibility have led to the introduction Biomedical, mechanical and
of some metastable β titanium alloys with elastic modulus
values as low as about 70–80 GPa [24–26]. However, there
material engineering of hip
has been, and still is, concern about too large elastic implants
modulus of implant alloys compared to that of compact
bone (30  GPa). The high difference in the modulus of The natural constitution of the hip joint, loading stresses,
elasticity of the alloy and of the bone causes stress incom- residual stresses and corrosion, mechanical design
patibility by stress, stress concentration and stress thresh- of human bearing and the materials which are avail-
old. The modulus of elasticity should be optimum which able define problems to solve for artificial hip implants.
assures better transfer of stresses between femoral stem Mechanical, chemical and physical properties as well as
with flange and a porous coating of alloy with gradient biocompatibility requirements define suitable solutions
porosity, which means a gradient-like distribution of for this complex problem. Typical components of hip
Young’s modulus. The modulus of elasticity depends on implants are shown in Figure 1.
the degree of porosity. The modulus of elasticity decreases As shown in Figure 1, a typical hip prosthesis consists
with increasing the porosity of coating from the implant of a femoral stem, a femoral head and socket. The femoral
surface to the bone. stem is usually manufactured from Co-Cr-Mo or Co-Ni-Cr-
Amongst metallic biomaterials, the elastic modulus of Mo alloys or from titanium base alloys (Ti-6Al-4V or new
Ti-6Al-4V alloy (E = 110  GPa) is much lower than that of one Ti-Nb-Zr). The head is made of highly polished Co-Cr-
316L (X3CrNiMnMo18-14-5-3)  stainless steel (E = 210  GPa) Mo alloy, of Al2O3 sintered ceramic composite or of stabi-
or Co-Cr-Mo alloy (E = 230  GPa). Other mechanical prop- lized ZrO2 with Al2O3 and yttrium oxide additives [10]. The
erties like hardness, ultimate tensile strength (UTS), metal-backed shell and the screws are made of titanium

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138      Choroszyński et al.: Biomaterials for hip implants

Table 2: Chemical composition of commercially pure titanium grades in wt.% according to ASTM F 67.

Designation   Ti   C (max)   Fe (max)   N (max)   O (max)   H (max)   Other

ASTM Grade 1  99.5   0.08   0.20   0.03   0.18   0.15  –

ASTM Grade 2  99.2   0.08   0.50   0.03   0.20   0.15  –
ASTM Grade 3  99.1   0.08   0.25   0.05   0.30   0.15  –
ASTM Grade 4  99.0   0.08   0.50   0.05   0.40   0.15  –
ASTM Grade 7  99.2   0.10   0.30   0.03   0.25   0.15   0.2 Pd

alloy Ti-6Al-4V or CP titanium (Tables 1 and 2). The socket the parameters of annealing according to the principle: the
(cup) is made of UHMWPE usually with metallic shell. higher the temperature of annealing, the larger the grain
Modular designs, where the stem and head are made of size and the smaller the mechanical properties. Mechani-
two materials, are common [11]. However, when two dif- cal properties of this alloy can be controlled over significant
ferent metallic alloys are applied, problems with galvanic range through hot and/or cold working and heat treatment.
corrosion should be considered and taken into account. The compacting and sintering technology is used to
produce ceramic components. The following technologi-
cal operations are heat or thermochemical treatments

Production technology including stress relaxation, annealing, super saturation,

ageing, carburizing and nitriding. Grinding and polish-
ing as the final machining are applied to obtain the final
Mechanical and biomedical properties depend on chemi-
shape and quality of a surface. The introduction of com-
cal, phase and microstructure composition. The technolog-
pressive stresses to the surface layer by thermochemical
ical processes which are applied influence characteristics
treatment (for example, by nitriding or carbonitriding) or
of the above materials. Therefore, knowledge about the
shot penning increases resistance to fatigue cracking. The
relationship between particular technological operations
majority of all the above considerations relate to metallic
and the properties considered is an important key to under-
components of hip implants; however, the contemporary
standing the technology of production of implant parts
modular structure of hip implants still needs to be devel-
and their expected features. Generally, metallic parts are
oped in the field of design, manufacturing technology and
produced by casting, metal forming (forging, rolling and
materials. The advanced metallic, ceramic, composite and
pressing), powder metallurgy (compacting and sintering)
polymer materials are an important key to the progress of
and various types of heat treatments and machining. The
hip prosthesis and of biomedical engineering in general.
most recent manufacturing method, i.e. “3D printing” as
an additive technology, is under development. Commonly,
metallic parts of hip implants are manufactured by forging.
Investment casting of hip stem is used as manufacturing Introduction of titanium and titanium alloys
method which is an alternative to forging. The main dis- for biomedical engineering
advantages of parts produced by investment cast are lower
mechanical properties than those of forged parts. Forged The selection of titanium and titanium alloys for hip
hip stems have a higher yield strength, tensile strength implants is determined by a combination of most favoura-
and fatigue strength than those made by a cast. This is due ble characteristics including high strength to weight ratio,
to the proper microstructure of alloy resulting from large outstanding resistance to corrosion by body fluids, high
plastic deformation during forging. The microstructure biocompatibility, low density and the capacity for joining
of cast alloys, called primary microstructure, is generally with bone, i.e. osteointegration. Titanium alloys have out-
worse due to non-uniformity like segregation of alloy- standing resistance to corrosion by body fluids, which is
ing elements and different grains size in different places. superior to that of stainless steels. Although titanium is
Mechanical properties of forged components are better highly reactive to oxygen, the creation of passive oxygen
than those produced by casting or 3D printing technology. layers and solid interstitial solution exhibits excellent cor-
The femoral stem is usually forged as α + β titanium phases rosion resistance in the human body environment. Sliding
at a temperature of 955°C. Forged stem parts are then contact should be avoided without modifying the surface
annealed at recrystallization temperature. The microstruc- by thermochemical diffusion treatment (such as nitriding
ture is either mill annealed or fully equiaxed depending on see, e.g. Figure 2).

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 Choroszyński et al.: Biomaterials for hip implants      139

the large difference between the atom size of titanium

and these elements. There is a reasonable difference in
solubility of these elements in α and β titanium [28].
Titanium and its alloys react with several interstitial ele-
ments including gaseous oxygen and nitrogen, and such
reactions occur at a temperature well below the respec-
tive melting points. This chemical affinity is used in the
thermochemical treatment of titanium alloys.
Commercially pure titanium of ASTM grades have low
strength but higher corrosion resistance than titanium
alloys. The addition of 0.2% Pd to commercially pure
titanium improves its strength and corrosion resistance
in active reducing media and is designated as Grade 7
(Table 2).
Figure 2: X-ray diffraction pattern of nitrided Ti-6Al-4V alloy with
Bragg-Brentana and grazing angle (α) diffraction geometry for com- Although interstitial elements increase the strength of
parison of phase composition versus X-ray depth of penetration (z), titanium, they are detrimental to toughness as measured
(for BB z = 5–18 μm; for α = 2, z = 1.1 μm; for α = 4, z = 2.4 μm; and for by the notch impact test. Therefore, when high toughness
α = 9, z = 4.8 μm) [27]. is desired for certain applications, the alloy should be pro-
duced with extra low interstitials (ELI). These alloys are
referred to as ELI alloys [27]. Strain hardening of titanium
Titanium exists in two allotropic crystallographic alloys is strongly sensitive to the rate of deformation.
forms: Tiα, which has the hexagonal closed packed crys- Increasing rate of deformation increases significantly the
tallographic structure, and Tiβ form, which has the body strain hardening rate. In order to obtain a large defor-
cubic (BCC) structure. In pure titanium, the α phase is mation of titanium alloys, the process is carried out in
stable up to 882°C. Above 882°C the α→β transit tem- hydraulic presses with a slow deformation rate. A slower
perature appears. The hexagonal α phase of pure Ti is deformation rate produces larger deformation of titanium
transformed in heating to the BCC β phase at a constant alloys without cracking. Plastic deformation is realized
temperature of 882°C. This phase transformation tem- with a dislocation slide mechanism suitable to the crystal-
perature depends on the chemical composition of tita- lographic lattice of both α and β phases [29]. The twining
nium alloys [28]. Commercially pure titanium which is system of deformation appears in both titanium phases as
unalloyed ranges in purity from 99.5 to 99.0% Ti (Table 1). well.
The main elements in unalloyed titanium are iron and The titanium α/β alloys are most often used in the
interstitial elements like carbon, oxygen, nitrogen and annealed condition. Their microstructure and mechani-
hydrogen [2, 4, 19, 21]. The chemical compositions of cal properties may differ depending on whether or
the principal grades of titanium are listed in Table 1. not prior plastic deformation was carried out above or
Commercially pure titanium can be considered as an α below the α/β phase transformation temperature. A
phase alloy in which the oxygen content determines the typical forging temperature of α/β Ti-6Al-4V is 955°C.
grade and strength. Titanium sponge due to metallurgi- An inert gas, e.g. argon can be introduced into one part
cal technology contains oxygen at a certain level, but its of the mould cavity. During the heat treatment, the high
amount is adjusted to modify the strength of commer- vacuum atmosphere is used, 10–5 torr). Above 535°C,
cially pure titanium. In this case, oxygen can be treated titanium absorbs oxygen and forms oxide compounds
as an “alloying element”. Carbon, nitrogen and hydro- (TiO, Ti2O3 and TiO2) and a solid solution as a subsurface
gen are present as metallurgical impurities in titanium. layer. All of them can improve mechanical properties
Oxygen within solution limits can be used as an intersti- from one side and nucleate surface and brittle cracks
tial strengthening element. Hydrogen is readily absorbed from another side. Titanium also absorbs hydrogen, and
by titanium alloys and is detrimental because it causes it is necessary to ensure that furnace atmospheres are
so-called hydrogen embrittlement by brittle needle- hydrogen free during melting, heat and thermochemi-
like precipitation of titanium hydrides (TiH2). Oxygen, cal surface treatments. Titanium alloys are particularly
nitrogen and hydrogen, on the other hand, can improve susceptible to galling, i.e. wear due to friction, during
biocompatibility. Nitrogen, carbon, oxygen, boron and hot or cold working, which causes surface damage.
hydrogen form interstitial solid solutions because of Therefore, proper lubricants should be applied during

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140      Choroszyński et al.: Biomaterials for hip implants

thermomechanical cold or hot working. During these discharge which produces single ions (in statu nascendi)
processes, graphite or molybdenum disulphide is used, according to the following reaction:
whereas glass powder may be used for a more severe
process like hot extrusion [27]. N2 → N2+ + N2+ + 4e

Only an active nitrogen in “statu nascendi” can

Physical metallurgy and surface layers diffuse to the metal surface layer of metal. The diffusion
of biocompatible titanium alloys for hip ion nitriding treatment (plasma nitriding) was carried
implants out in controlled atmosphere (containing a mixture of
nitrogen ions and argon) at a temperature of 700°C. The
Titanium alloys are sensitive to contact in friction couple phase composition varies versus thickness of the surface
due to sticking or galling, which may lead to fretting. For layer, and some level of residual stresses was measured
this reason, titanium alloys have low resistance to fretting. (about −522 MPa) with GID-sin2ψ method [30]. The quali-
Fretting occurs when two surfaces are in contact and small tative X-ray phase analysis showed the dominating phase
amplitude relative oscillation motion is present. Fretting component as Tiα, TiN and Ti2N (Figure 2). The two latest
damage in titanium alloys can significantly reduce fatigue nitrides appear in a thin surface layer of a nitrided Ti-6Al-
life. Fretting is a major concern for hip implants in joints 4V alloy with the plasma thermochemical process. The
between femoral stems and heads. investigated surface layer was exposed with X-ray grazing
Fretting corrosion is a serious problem in implants angle (α) diffraction geometry with incident beam angle
because it is the main mechanism of gradual release of α = 2 and α = 4°. The applied X-ray diffraction geometries
metal ion to different tissues in the body. Fretting corrosion are destined for thin surface layer analysis with differ-
and abrasive wear cause pain and excessive ­accumulation ent thicknesses. This means that very thin surface layer
of wear particles which results from prosthesis losses. The thickness of 2 and 4  μm consists of TiN and Ti2N, and
extensive release of metal ions from hip prosthesis can deeper layers as a substrate under them consist of hex-
result in adverse biological reactions [12, 19]. agonal phase Tiα(N) as a solid solution with a gradient-
Two primarily problems arise when attempting to coat like nitrogen distribution (Figure 2). Similar experiments
titanium alloy with TiN, TiC and TiCN layers. The thermal and examinations carried out on CP4 titanium [18] under
expansion coefficients of the coating and of the titanium a little bit different conditions confirmed phase composi-
substrate are different, and as a result, large thermal tion and compressive residual stresses.
stresses are generated at the interface during the coating
deposition process [30]. Such coating also has a differ-
ent microstructure, crystallographic structure, differ- Classification of titanium alloys
ent mechanical properties (strength, hardness, modulus
of elasticity etc). The coating layer of the femoral head Titanium alloys are classified into categories according
should not be too hard. Under heavy load and residual to the microstructure and phase composition (structure)
stress, the coated layer will be cracking. These stresses can retained at room temperature after solidification and
lead to cracks at the interface coating/substrate. In addi- other metallurgical processes. Both characterizations
tion, chemical reactions between the coating and titanium depend on heat and various kinds of thermomechanical
alloy can weaken the metal in the vicinity of the interface, treatments. According to the phase composition (as struc-
reducing strength and corrosion resistance of the coating ture composition), titanium alloys can be divided into
system. Most advanced coatings were elaborated with the 1. α alloys
application of hydroxyapatite and some other ceramic 2. near α alloys
compounds [19, 31]. 3. α + β alloys
Therefore, diffusion thermochemical treatment is 4. β alloys
a better solution in order to produce hard, highly resist- 5. near β alloys
ant to wear and gradient like mechanical properties 6. metastable β alloys
versus depth from the surface. Here is an example of a
­thermochemical ion nitriding of Ti-6Al-4V alloy (Figure 2). The most known Ti-6Al-4V titanium alloy contains 6 wt.%
Very clean nitrogen (N2) was introduced to vacuum furnace aluminium and 4 wt.% vanadium. It was invented in 1946
chamber. Under high voltage, electrical discharge occurs in the USA as a most advanced alloy for aeroplane and
and the nitrogen is dissociated, ionized in the form of glow cosmos industry applications. Soon afterwards, this alloy

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 Choroszyński et al.: Biomaterials for hip implants      141

was experimentally introduced as a good biocompat- modulus than alloy Ti-6Al-4V, excellent hot and cold work-
ible alloy for medical application. Gradually, aluminium ability and superior corrosion resistance. The Ti-13Nb-13Zr
and later vanadium were substituted by elements more alloy is a metastable beta titanium alloy developed for use
friendly for the human body (Table 3). A new generation in biomedical implants that combines a high biocompat-
of titanium alloys with niobium was introduced in 1979 [5, ibility, superior corrosion resistance, high strength, excel-
25, 26, 32–34]. New β or near β titanium alloys contain bio- lent hot and cold workability and lower elastic modulus.
compatible alloying elements: Nb, Zr and Ta. They have Mechanical properties of this alloy can be controlled over
a lower modulus of elasticity as compared to α + β alloys. significant range through hot working, cold working and
The β alloys have excellent formability, cold rolling capa- heat treatment. The mechanical properties of Ti-13Nb-13Zr
bilities, good ductility and formability. The main disad- can vary by thermomechanical treatment. This alloy con-
vantage of β alloys in comparison with α + β alloys is their tains a high percentage of high-density alloying elements.
higher density. Most recently developed alloys based on Because of the high density of zirconium and niobium,
the Ti-Nb-Zr-Ta alloying elements appeared as β alloy has there is a problem of segregation during melting and
the lowest modulus of elasticity, E = 70 GPa [3, 24]. solidification of alloys containing these elements.
Alloy Ti-13Nb-13Zr was originally developed for Also, because of the high density of niobium and zir-
medical implant applications [24]. This alloy combines conium, special techniques of mixing liquid metal during
a high biocompatibility, high strength, lower elastic melting and casting process are required to prevent seg-
regation of alloying elements. Niobium and zirconium
have larger atomic diameter than titanium. Special ther-
Table 3: Selected experimental and applied titanium alloys for
mochemical treatment which provides point defects and
implant applications.
dislocations should be applied to increase the diffusion
Alloy designation and type Developed in rate of alloying elements in order to obtain the proper
response during homogenization treatment. Segrega-
α + β alloys
tion of alloying elements cannot be tolerated in metal-
Ti-6Al-4V USA
Ti-6Al-4VELI USA lic implants. Segregation of alloying elements decreases
Ti-6Al-7Nb Switzerland resistance to corrosion and fatigue crack initiation, lowers
Ti-5Al-2.5Fe Germany resistance to an impact load and fracture resistance and
Ti-3Al-2.5V USA decreases biocompatibility. The newest development of
Ti-15Zr-4Nb-2Ta-0.2Pd Japan
titanium alloys is directed to Ti-Au ­composition with an
Ti-5Al-3Mo-4Zr Japan
Ti-15Sn-4Nb-2Ta Japan
expectation of better mechanical and biomedical proper-
β alloys ties. Another titanium base alloy with nickel, nitinol, is
Ti-15Mo-5Zr-3Al Japan also an important biomaterial [35, 36].
Ti-29Nb-13Ta-4.5Zr Japan
Ti-13Nb-13Zra USA
Ti-12Mo-6Zr-2Fe USA
Ti-16Nb-10Hf USA Cobalt base alloys for hip implants
Ti-35Nb-7Zr-5Ta USA
Ti-15Mo-2.8Nb-0.2Si-0.26O USA Cobalt-chromium alloys have good resistance to pitting
and crevice corrosion in the human body. The main cobalt
a
The only alloy with homogeneous microstructure is single-phase β.
Alloy with segregation of Nb and Zr is not acceptable. Segregation of alloys (Table 4) used for hip implants are
alloying elements (Nb and Zr) causes not homogeneous microstruc- –– ASTM F75, (Co-28Cr-6Mo) casting alloy
ture sensitive to corrosion and fracture. –– ASTM F90, (Co-20Cr-15W-10Ni) wrought alloy

Table 4: Chemical composition in wt.% of selected cobalt base alloys used for hip implants (Co balance).

ASTM   UNS no.   Cr   Mo   Ni   Fe   C   Si   Mn   W   P   S  Other

designation

F75   R30075   27.0–30.0   5.0–7.0   1.0   0.75   0.35   1.0   1.0   0.20   0.020   0.01  0.25 N, 0.30 Al
F90   R3065   19.0–21.0   –   9.0–11   3.0 max   0.05–0.15   0.40   0.40   14.0–16.0   0.040   0.03  –
F562   R30563   19.0–21.0   9.0–10.5   33.0–37.0   1.0 max   0.025 max   0.15   0.15   –   0.015   0.01  1.0 Ti
F563   R30563   18.0–22.0   3.0–4.0   15.0–25.0   4.0–6.0   0.05   0.50   1.0   3.0–4.0   –   0.01  0.50–3.50 Ti
F799   R31537   26.0–30.0   5.0–7.0   1.0   0.75   0.35   1.0   1.0   –   –   –  0.25 N

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142      Choroszyński et al.: Biomaterials for hip implants

Table 5: Chemical compositions (in wt.%) of austenitic stainless steels used for surgical implants according to the ASTM specifications
(Fe balance).a

ASTM   C  Cr   Ni   Mn   Mo   Cu  N   P  S  Other

designation

F138   0.03   17.00–19.00   13.0–15.00   2.00   2.25–3.00   0.50  0.10   0.025   0.010  –
F1314   0.03   20.50–23.50   11.50–13.50   4.00–6.00   2.00–3.00   0.50  0.20–0.40   0.025   0.010  0.10–0.30 Nb; 0.10–0.30 V
F1586   0.08   19.50–22.00   9.00–11.00   2.00–4.25   2.00–3.00   0.25  0.25–0.50   0.25   0.010  0.25–0.80 Nb
F2229   0.08   19.00–23.00   0.10   21.00–24.00   0.50–1.50   0.25  0.90 min   0.03   0.010  0.95 N

Single values are maximum values unless otherwise indicated.

a

–– ASTM F999, (Co-28Cr-6Mo) thermomechanically 3. M6C carbides, where “M” stands for tungsten or
processed molybdenum; these carbides form when the tungsten
–– ASTM F562, Co-35Ni-20Cr-10Mo wrought alloy or molybdenum content exceeds about 5 at.%.
–– ASTM F 1058 (Co-20Cr-15, 5 Ni-7Mo-Fe) wrought alloy
–– MP35N, (35Co-35Ni-20Cr-10Mo) thermomechanically Components made of cobalt alloys are designed as
processed perfect spherical head of hip bearing so that the metal
always articulates against a low friction plastic (e.g.
UHMWPE or high cross-linking polyethylene), which
Biophysics and physical metallurgy of cobalt provides smooth relative movement, small friction and
alloys minimum abrasive wear. The recent reports on cobalt
alloys applied for hip implants show an easy diffusion
Cobalt is beneficial for humans because it is a component of Co ions from the hip implant to body fluids. This type
of vitamin B12 (cobalamin), which is essential for human of implementation with cobalt alloy implants caused
health. However, too high concentrations of cobalt may excessive concentration of Co in blood [20]. Therefore,
be toxic to health. A cobalt-based alloy was first used as a some limitations in this type of application have been
material for hip implants in the USA in 1936. At tempera- prepared.
tures below 417°C cobalt exhibits a hexagonal close-packed
structure. Between 417°C and its melting point of 1493°C,
cobalt has a face-centred cubic (FCC) structure. The melting Austenitic stainless steels
point of cobalt is 1768°C. The elastic modulus of cobalt is
about 210  GPa in tension and about 183  GPa in compres- The main components of stainless steels are iron, nickel
sion. Cobalt has a density of 8.90 g/cm3. Typically, the and chromium. Generally, stainless steels are divided into
microstructure of cobalt-based alloys consists of FCC as (γ) three groups: ferritic, martensitic (tool steels) and austen-
phase as matrix and various types of carbides. A strength- itic. Only the last type of stainless steels called bio-steels
ening in cobalt-based alloys is obtained primarily through a is applied for a hip prosthesis for short-term use. Auste-
combination of solid solution strengthening (by Cr, Mo and nitic stainless steels were first used as a material for hip
Fe atoms) and carbide precipitation. Strength and tough- implants in the USA in 1926.
ness depend on the amount of solved foreign atoms and Nevertheless, iron ions are important components of
amount, size and distributions of carbides. A fine disper- blood; other chemical components are rather harmful to
sion of carbides contributes significantly to the strength of human body.
these alloys. Dislocation movement is strongly impeded by Austenitic stainless steels are used for implant appli-
carbide precipitations. Carbide precipitations are barriers cations because they are relatively inexpensive. Passiva-
for dislocation movements. This carbon content in these tion of stainless steel implants is enhanced by nitric acid.
alloys has a significant effect on the number of carbides. In Austenitic stainless steels are not sufficiently corrosion
general, three main types of carbides can be present in the resistant for long-term use as an implant material. Pitting
microstructure of cobalt-based alloys [8, 14–17]: corrosion in austenitic stainless steels is usually caused
1. M23C6 carbides, where “M” is mostly chromium but by chlorine ions and starts at nonmetallic inclusions
can be substituted by tungsten and molybdenum; (sulphur inclusions) and other heterogenic places. Molyb-
2. MC carbides, where M stands for the reactive metals denum is added to stainless steels usually in amounts of
tantalum, titanium, zirconium and niobium; 2–3% to increase resistance to pitting corrosion in saline

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 Choroszyński et al.: Biomaterials for hip implants      143

environments. Nitrogen-strengthened alloys are used for The capacity for joining implant with the bone, i.e. oste-
the bone plate and bone screws. ointegration, which is direct bone anchorage to an implant
Austenitic stainless steels have excellent formability, into bone with no fibrous capsule interface, makes it pos-
and their response to deformation depends on the nickel sible to transmit the loading forces directly to the bone.
content. Formability increases with an increase in the All the beneficial passive layers on metals can be
content of nickel. Magnetic alloys should not be used in mechanically damaged by the fretting of metal against
the human body because they could become dislodged in metal.
the strong magnetic field of magnetic resonance imaging. Titanium alloys are used for hip implants due to excel-
Pitting corrosion in the stainless steels occurs when the lent combination of mechanical properties, low density,
protective film is broken, exposing the steel to Cl− ions. Aus- acceptable tissue tolerance, high strength to weight ratio,
tenitic stainless steels for hip implants can be divided into outstanding resistance to corrosion by body fluids, high
1. low carbon stainless steels biocompatibility, low density and nonmagnetic properties.
2. nitrogen-strengthened stainless steels Titanium induces the formation of a fibrous tissue
3. nickel-free stainless steels barrier when placed in contact with a healthy bone. This
permits the bone to grow closely on the surface of the
Examples of major ASTM austenitic stainless steels for femoral stem and fill pores that have been deliberately
implant materials: introduced to facilitate bone ingrowths.
Contaminations of titanium alloys by interstitial ele-
Low carbon stainless steels: ASTM F138/139 316 L, ments such as hydrogen and oxygen during fabrication
(21Cr-10Ni-3Mn-2.5 Mo). This steel contains 0.25–0.50% N. (melting, thermomechanical treatment and thermochemi-
cal surface hardening) must be avoided because these ele-
Nitrogen-strengthened stainless steels: ASTM 1314 ments have an embrittling effect on titanium.
(22Cr-12, 5Ni-5Mn-2.5Mo-0.30 N). This steel contains 0.20– In the presence of hydrogen, titanium hydrides (TiH2)
0.40% N. may form into long thin needles in titanium alloys and
these hydrides decrease resistance to fracture.
Nickel free stainless steel and nitrogen-strengthened Austenitic stainless steel, particularly nickel-free
steels: ASTM 1314 F2229 (23Mn-21 Cr-1Mo –0.95N). stainless steel with nitrogen strengthened like ASTM 1314
F2229 (23Mn-21Cr-1Mo-0.95N), can be used for some ele-
The substitution of nickel atoms is important due to its ments of hip implants.
harmful activity in the human body. Because of that, Cobalt-chromium alloys are the most commonly used
Ni-free stainless steels were elaborated (Table 5). metals for current metal on polymer implants. A typical
microstructure of cobalt base alloys consists of FCC (γ)
phase matrix and carbides of various types.
Summary Hydroxyapatite is widely used as bioactive porous
coating of the femoral stem and the metallic shell in hip
The review, as presented above, i.e. titanium and cobalt implants.
alloys, bio-steels, their specific treatments, surface layers A special type of polyethylene, i.e. special grade
and coatings on alloys used for hip prosthetic can be sum- UHMWPE with additional cross linking bonding, is
marized as follows: widely used (as socket) in hip implants as the load-bear-
The synergy of some branches of science and techno- ing material (in hip implants with combination metal on
logy, i.e. medicine (surgery), mechanical design and polymer).
material science and technology has led to progress and The final decision about the type and material of hip
achievements in hip implants. implants made in the hospital by medics is supported by
All of the chemical elements of the materials applied many additional factors like accessibility, availability of
in implants are building components of the human body, the material, the patient’s weight and age, etc.
but some of them are even poisonous and others, like
aluminium, vanadium and nickel, are classified as toxic
elements. Conclusions
Biomedical implant reliability depends largely on the
corrosion, abrasive wear and fatigue strength/resistance 1. The synergy of medicine, biochemistry, biophys-
of the materials used in production technology. ics, mechanical engineering, materials science and

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144      Choroszyński et al.: Biomaterials for hip implants

informatics succeeds in achieving real progress in Author contributions: All the authors have accepted
orthopaedic surgery of hip joint implants. responsibility for the entire content of this submitted
2. Although the majority of chemical elements of the manuscript and approved submission.
materials applied to make implants are building com- Research funding: The results of research and this paper
ponents of the human body, it is usually harmful if were supported by the Faculty of Metals Engineering and
their concentrations in some tissues, bone or in body Industrial Computer Science, Department of Physical
liquids are over the natural level. and Powder Metallurgy of AGH-University of Science and
3. The fatigue and stress corrosion damage are the major Technology in Krakow under project no 11.11.110.299.
causes for the failure of orthopaedic implants. The Employment or leadership: None declared.
fatigue strength and yield point ratio of biomateri- Honorarium: None declared.
als applied are small and range between 0.3 and 0.7, Competing interests: The funding organization(s) played
which, with additional large safety coefficient, cause no role in the study design; in the collection, analysis, and
mechanical strength and total reduced stress calcula- interpretation of data; in the writing of the report; or in the
tions to be rather complex and difficult. decision to submit the report for publication.
4. The majority of parts of hip joint implants are made
of metallic materials due to heavy and cyclic loaded
bearings. Additionally, they work in the bioactive
environment. Titanium alloys are most advanced References
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