Part III: State‐of‐the‐art Advances/ Production/ Synthesis
Daniel Cook
Introduction
As mentioned in previous portions of this paper, Magnesium is an ideal candidate as a biodegradable
material. It is highly biocompatible (approximately three‐hundred milligrams per day is the
recommended daily intake), has a high primary stability, and has a superior strength to weight ratio.
Even with such promising characteristics Magnesium has yet to make a significant contribution in the
field biomaterials. A major factor preventing its application is its high rate of corrosion in‐vivo. High rates
of corrosion are the source of two problems. First, magnesium corrodes in‐vivo through the following
equation:
2 ↔
As can be seen from this one mole of magnesium produces one mole of hydrogen gas, causing a large
accumulation of subcutaneous gas bubbles. The second issue with high corrosion rates is the tissue the
implant is supporting will not have sufficient time to heal before the implant completely corrodes. This
is most evident in bone fracture and stent use. Both bone and arteries require approximately six weeks
to fully heal, meaning the implant must last this amount of time. This section of the paper will look at
what methods are being investigated to control the problem of rapid corrosion.
Alloying
Alloying magnesium with more corrosion resistant materials is the first method being investigated. Two
of the main alloys currently being researched are WE43 and AZ91D. The composition of these alloys are
as follows:
WE43
Element Weight Percent
Yttrium 4.11
Neodymium 2.28
Rhenium 0.98
Zirconium 0.45
Dysprosium 0.27
Magnesium 91.91
AZ91D
Element Weight Percent
Aluminum 8.1
Zinc 1
Silicon 0.3
Manganese 0.13
Magnesium 90.47
There are two methods used to produce these alloys, depending on the intended application. The first
method is die casting. This method is used when the implant needs to be a bulk metal, such as when
the implant is used for bone repair. Die casting involves heating the metals until they reach a molten
state. Pressure is then used to force this liquid into a mold where it cools and hardens, forming the
alloy.
The second method for production is electron beam physical vapor deposition. This method is preferred
when the alloy must be very thin (micrometers range), or when the implant must have a very specific
surface morphology. These requirements are common to stent use. In this method electrons ejected
from a charged tungsten filament bombard the metals, causing them to vaporize. The vapor containing
the metals then precipitates, forming a thin solid alloy.
The purpose of adding these metals to pure magnesium is that they provide electrochemical protection,
as well as acting as hardeners. From an electrochemical perspective, all of the listed alloying metals are
more noble than magnesium thus providing cathodic protection. From a physical point‐of‐view many of
the metals, specifically aluminum, zinc, and the rare earth metals cause solid solution strengthening.
Solid solution strengthening helps prevent dislocations from easily sliding, thus increasing the yield
strength of the material.
The benefit of alloying can be seen by looking at table x which displays the experimental corrosion rate
of both WE43 and AZ91D tested in simulated body fluid at thirty seven degrees Celsius.
Alloy Corrosion Rate (mm/year)
AZ91D 2.8
WE43 6.9
Pure Magnesium 105
Coatings
It is immediately apparent that the addition of alloying elements significantly decreases the rate of
corrosion. However even with such drastic drops in corrosion rate, some issues still remain. While bulk
metal applications can typically be made thicker to increase the amount of time before total
degradation, applications of thin films typically have very tight space requirements meaning increasing
the thickness of the implant is not viable. This is where another, more recent, research topic in
magnesium biomaterials has taken hold. This new topic involves the formation of a very thin coating on
top of the magnesium implant.
The idea b behind providding a thin surface coatingg on top of thee magnesium m or magnesiu um alloys is to o
make the coating mate erial more corrosion resisttant than stanndard magnesium. This coating will theen
corrode fiirst, saving th
he magnesium m implant from m immediatee corrosion.
The first ccoating being investigated is magnesium m hydroxide. This coatingg is very easy tto synthesizee on
magnesium thin films. It is formed by soaking a magnesium tthin film in on ne molar sodiium hydroxid de
solution for twenty‐fou ur hours. The
e coating is fo
ormed througgh the followiing reaction:
2 →
Experimental corrosion n rate measurements for tthin film maggnesium treatted with the h hydroxide coaating
showed a significant de ecrease in corrosion, even n when comp ared to untreeated alloys, ssummarized iin
table y.
Material Corrosiion rate (mmm/year)
Pure Maggnesium 105
AZ91D 2.8
Magnesiu um with Hydro oxide Coatingg 0.252
Another b benefit to the
e hydroxide cooating is not oonly the biocoompatibility o
of the coatingg, but it actuaally
increases cell proliferation on its surface. This caan be seen in figure z:
The hydrooxide coating accomplishes this cell pro
oliferation by decreasing h hydrogen gas evolution, heelping
to keep th
he pH in a viable range, as well as proviiding a betterr surface for ccell adhesion.. While the
coating sttill lacks the cell density off the simulate des a significant improvement
ed body fluid, it still provid
over untre eated magne esium.
The secon nd coating garnering atten ntion is a magnesium fluor ide coating. TThis coating iis produced b by
first applyying a hydroxide coating ass described above. Once tthis coating iss applied to the implant, itt is
then imm mersed in a forrty percent hyydrofluoric accid solution foor ninety‐six hours. The reeaction forming
this coatinng is:
2 →
This coating is still in itts infancy stagges in terms o
of being usedd as a corrosio on inhibitor, sso there is very
porting corrossion rate evid
little supp dence. Howevver some elecctrochemical analysis has been done. TThe
following figure compaares the breakdown voltagges of pure m magnesium to the fluoride coated
magnesium:
This figure
e shows that the breakdow wn voltage is much higherr for the fluorride coating th han the uncoated
magnesium. The coate ed sample alsso has a lower current dennsity througho out the rangee of voltages
Both these factor generally correspond
applied. B d to a lower coorrosion ratee in practice.
In addition to the theo oretical reduction in corrossion rate, the fluoride coatting also provvides a mechaanical
advantage e. In applicattions such as stents, the co
onstant mechhanical strain put on the im mplant from tthe
expandingg and contraccting of blood d vessels causse cracks to foorm in the coating. These cracks allow the
environment to by‐passs the coatingg and directly attack the puure magnesiu um implant. W With the fluo
oride
coating hoowever, these e cracks naturally passivatte and form t he hydroxidee coating explained above. This
can be illu
ustrated as:
Conclusiion
ng and the applications of ccoatings to puure magnesiu
As can be seen, alloyin um can signifiicantly alter tthe
rate of corrosion to an acceptable le
evel. These aadvances givee great promise to the futu ure of magnesium
as a biode
egradable maaterial. Howeever more ressearch must bbe done beforre it reaches aa commercial
stage. Ad
dditional corro
osion data for the coatingss must be obttained, as weell as testing o
of the alloys aand
coatings in‐vivo to prove biocompatibility.