U.S. patent application number 14/395709 was filed with the patent office on 2015-03-19 for magnesium-aluminum-zinc alloy, method for the production thereof and use thereof.
The applicant listed for this patent is BIOTRONIK AG. Invention is credited to Joerg Loeffler, Heinz Mueller, Peter Uggowitzer.
Application Number | 20150080998 14/395709 |
Document ID | / |
Family ID | 48672636 |
Filed Date | 2015-03-19 |
United States Patent
Application |
20150080998 |
Kind Code |
A1 |
Mueller; Heinz ; et
al. |
March 19, 2015 |
MAGNESIUM-ALUMINUM-ZINC ALLOY, METHOD FOR THE PRODUCTION THEREOF
AND USE THEREOF
Abstract
A magnesium alloy and to a method for the production thereof and
implants made thereof. The magnesium alloy includes up to 6.0% by
weight Zn, and preferably 2.0 to 4.0% by weight Zn, 2.0 to 10.0% by
weight Al, and preferably 3.0 to 6.0% by weight Al, where % by
weight Al.gtoreq.% by weight Zn shall apply, the remainder being
magnesium containing impurities, which promote electrochemical
potential differences and/or the formation of precipitations and/or
intermetallic phases, in a total amount of no more than 0.0063% by
weight of Fe, Si, Mn, Co, Ni, Cu, Zr, Y, Sc or rare earths having
the ordinal numbers 21, 57 to 71 and 89 to 103, Be, Cd, In, Sn
and/or Pb as well as P, and the matrix of the alloy is solid
solution hardening due to Al and An and is also particle hardening
due to the intermetallic phases formed of Mg and Al.
Inventors: |
Mueller; Heinz;
(Diedrichshagen, DE) ; Uggowitzer; Peter;
(Ottenbach, CH) ; Loeffler; Joerg; (Greifensee,
CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BIOTRONIK AG |
Buelach |
|
CH |
|
|
Family ID: |
48672636 |
Appl. No.: |
14/395709 |
Filed: |
June 24, 2013 |
PCT Filed: |
June 24, 2013 |
PCT NO: |
PCT/EP2013/063110 |
371 Date: |
October 20, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61664224 |
Jun 26, 2012 |
|
|
|
Current U.S.
Class: |
623/1.1 ;
148/420; 148/538; 148/557 |
Current CPC
Class: |
A61L 27/047 20130101;
C22C 23/02 20130101; C22F 1/06 20130101; A61L 27/58 20130101; A61F
2/82 20130101; A61L 31/022 20130101; A61L 31/148 20130101 |
Class at
Publication: |
623/1.1 ;
148/538; 148/420; 148/557 |
International
Class: |
C22F 1/06 20060101
C22F001/06; C22C 23/02 20060101 C22C023/02; A61F 2/82 20060101
A61F002/82 |
Claims
1. A magnesium alloy having improved mechanical and electrochemical
properties, comprising: less or equal 4.0% by weight Zn, 2.0 to
10.0% by weight Al, the alloy content of Al in % by weight being
greater than or equal to the alloy content of Zn in % by weight,
the remainder being magnesium containing impurities, which promote
electrochemical potential differences and/or the formation of
precipitations and/or intermetallic phases, in a total amount of no
more than 0.0063% by weight of Fe, Si, Mn, Co, Ni, Cu, Zr, Y, Sc or
rare earths having the ordinal numbers 21, 57 to 71 and 89 to 103,
Be, Cd, In, Sn and/or Pb as well as P, wherein the matrix of the
alloy is solid solution hardening due to Al and Zn and is also
particle hardening due to the intermetallic phases formed of Mg and
Al.
2. The magnesium alloy according to claim 1, wherein the content of
Zn less or equal 2.0% by weight, in particular preferably less or
equal 1.0% by weight and/or the content of Al is 2.0 to 8.0% by
weight, preferably 3.0 to 8.0% by weight and still more preferably
3.0 to 6.0% by weight.
3. The magnesium alloy according to claim 1, wherein individual
impurities in the total sum of impurities amount to the following
in % by weight: Fe, Si, Mn, Ni, Co, Cu each with <0.0005; Zr; Y
each with <0.0003; and P<0.0002.
4. The magnesium alloy according to claim 1, wherein impurity
elements Fe, Si, Mn, Co, Ni, and Cu together total no more than
0.003% by weight.
5. The magnesium alloy according to claim 1, wherein the alloy has
a fine-grained microstructure having a grain size of no more than
7.5 .mu.m.
6. The magnesium alloy according to claim 1, having a tensile
strength of >275 MPa, a yield point of >200 MPa, and a yield
ratio of <0.8, wherein the difference between the tensile
strength and yield point is >50 MPa, and the mechanical
asymmetry is <1.25.
7. A method for producing a magnesium alloy having improved
mechanical and electrochemical properties, comprising: a)
generating a high-purity magnesium by vacuum distillation; b)
generating a billet of the alloy by synthesis of the high-purity
magnesium with less or equal 4.0% by weight Zn, 2.0 to 10.0% by
weight Al, wherein the alloy content of Al in % by weight is
greater than or equal to the alloy content of Zn in % by weight,
the remainder being magnesium containing impurities, which promote
electrochemical potential differences and/or the formation of
precipitations and/or intermetallic phases, in a total amount of no
more than 0.0063% by weight of Fe, Si, Mn, Co, Ni, Cu, Zr, Y, Sc or
rare earths having the ordinal numbers 21, 57 to 71 and 89 to 103,
Be, Cd, In, Sn and/or Pb as well as P, wherein the matrix of the
alloy is solid solution hardening due to Al and Zn and is also
particle hardening due to the intermetallic phases formed of Mg and
Al; c) homogenizing the alloy by annealing at a temperature between
150.degree. C. and 450.degree. C. with a holding period of 4 to 40
hours; d) forming of the homogenized alloy in the temperature range
between 200.degree. C. and 400.degree. C.
8. The method according to claim 7, wherein the billet content of
Zn is less or equal 2.0% by weight, and/or the content of Al is 2.0
to 8.0% by weight.
9. The method according to claim 7, wherein individual impurities
in the total sum of impurities amount to the following in % by
weight: Fe, Si, Mn, Ni, Co, Cu each with <0.0005; Zr, Y each
with <0.0003; and P<0.0002.
10. The method according to claim 7, wherein Fe, Si, Mn, Co, Ni,
and Cu together total no more than 0.003% by weight.
11. The method according to claim 7, wherein the forming process
comprises extrusion, equal channel angular extrusion (EACE) and/or
a multiple forging process.
12. The method according to claim 7, wherein steps c) and d) are
repeated at least once.
13. The method according to claim 7, wherein step c) is performed
at a temperature between 250.degree. C. and 450.degree. C. and/or
step d) is performed at a temperature between 225.degree. C. and
400.degree. C.
14. A biodegradable implant formed from the alloy of claim 1.
15. A biodegradable implant according to claim 14, comprising one
of a stent, an implant for fastening and temporarily fixing tissue
implants and tissue transplantations, an orthopedic implant, a
dental implant, and a neuroimplant.
16. (canceled)
17. (canceled)
18. The magnesium alloy according to claim 1, wherein the alloy has
a fine-grained microstructure having a grain size of <5
.mu.m.
19. The magnesium alloy according to claim 1, wherein the alloy has
a fine-grained microstructure having a grain size of <2.5
.mu.m.
20. The magnesium alloy according to claim 1, having a tensile
strength of >300 MPa, a yield point of >225 MPa, and a yield
ratio of <0.75, wherein the difference between the tensile
strength and yield point is >100 MPa, and the mechanical
asymmetry is <1.25.
21. The method according to claim 7, wherein the billet content of
Zn is less or equal 1.0% by weight and/or the content of Al is 3.0
to 6.0% by weight.
Description
PRIORITY CLAIM
[0001] This application is a U.S. National Phase under 35 U.S.C.
.sctn.371 of International Application No. PCT/EP2013/063110, filed
Jun. 24, 2013, which claims priority to U.S. Provisional
Application No. 61/664,224, filed Jun. 26, 2012.
FIELD OF THE INVENTION
[0002] A field of the invention relates to a magnesium alloy and to
a method for the production thereof and to the use thereof.
Magnesium alloys of the invention are applicable to implants,
including cardiovascular, osteosynthesis, and tissue implants.
Example applications include stents, valves, closure devices,
occluders, clips, coils, staples, implantable regional drug
delivery devices, implantable electrostimulators (like pacemakers
and defibrillators), implantable monitoring devices, implantable
electrodes, systems for fastening and temporarily fixing tissue
implants and tissue transplantations. Additional example
applications include implantable plates, pins, rods, wires, screws,
clips, nails, and staples.
BACKGROUND
[0003] Magnesium alloy properties are determined by the type and
quantity of the alloying elements and impurities as well as the
production conditions. The effects of the alloying elements and
impurities on the properties of the magnesium alloys have been
known to artisans. However, determining the properties of binary or
ternary magnesium alloys for use as implant materials remains
complex.
[0004] The alloying element used most frequently for magnesium is
aluminum. Aluminum provides increased tensile strength due to solid
solution and precipitation hardening and fine grain formation, but
also in microporosity. Moreover, in the melt aluminum shifts the
iron precipitation boundary toward drastically lower iron contents
at which the iron particles precipitate or form intermetallic
particles together with other elements.
[0005] Calcium exhibits a pronounced grain refining effect and
worsens the castability and corrosion resistance.
[0006] Undesirable accompanying elements in magnesium alloys
include iron, nickel, cobalt and copper, which cause a considerable
increase in the corrosion tendency due to the electropositive
nature thereof.
[0007] Manganese can be found in all magnesium casting alloys and
binds iron in the form of AlMnFe precipitations, whereby the
formation of local elements is reduced. On the other hand,
manganese is not able to bind all the iron, and therefore a
remainder of iron and a remainder of manganese are always left in
the melt.
[0008] Silicon lowers the castability and viscosity, and as the
content of Si rises, a worsened corrosion behavior is to be
expected. Iron, manganese and silicon have a very high tendency to
form an intermetallic phase. The electrochemical potential of this
phase is very high and can thus act as a cathode controlling the
corrosion of the alloy matrix.
[0009] As a result of solid solution hardening, zinc improves the
mechanical properties and results in grain refining, however it
also leads to microporosity with a tendency toward hot cracking
starting at a content of 1.5 to 2% by weight in binary Mg--Zn and
ternary Mg--Al--Zn alloys.
[0010] Alloying additions made of zirconium increase the tensile
strength without lowering the expansion and lead to grain refining,
but also to a strong impairment of dynamic recrystallization, which
is manifested in an increase of the recrystallization temperature
and therefore requires high energy expenditure. Moreover, zirconium
cannot be added to melts containing aluminum and silicon because
the grain refining effect is lost.
[0011] Rare earths such as Lu, Er, Ho, Th, Sc and In all exhibit a
similar chemical behavior and form eutectic systems with partial
solubility on the magnesium-rich side of the binary phase diagrams
such that precipitation hardening is possible.
[0012] The addition of further alloying elements, in conjunction
with the impurities, is known to cause the formation of different
intermetallic phases in binary magnesium alloys. For example, the
intermetallic phase Mg.sub.17Al.sub.12 forming at the grain
boundaries is brittle and limits the ductility. As compared to the
magnesium matrix, this intermetallic phase is more noble and able
to form local elements, whereby the corrosion behavior worsens.
[0013] In addition to these influencing factors, the properties of
the magnesium alloys also decisively depend on the metallurgical
production conditions. Conventional casting methods automatically
introduce impurities when adding, by alloying, the alloying
elements. The prior art (U.S. Pat. No. 5,055,254 A) therefore
defines tolerance limits for impurities in magnesium casting
alloys, which, for example for a magnesium-aluminum-zinc alloy
containing approximately 8 to 9.5% by weight Al and 0.45 to 0.9% by
weight Zn, mentions tolerance limits of 0.0015 to 0.0024% by weight
Fe, 0.0010% by weight Ni, 0.0010 to 0.0024% by weight Cu and no
less than 0.15 to 0.5% by weight Mn.
[0014] Tolerance limits for impurities in magnesium and the alloys
thereof as well as the production conditions are mentioned in many
known documents and listed as follows in % by weight:
TABLE-US-00001 Alloy Production State Fe Fe/Mn Ni Cu Pure no
information 0.017 0.005 0.01 Mg AZ 91 Die casting F 0.032 0.005
0.040 High-pressure die casting 0.032 0.005 0.040 Low-pressure die
casting 0.032 0.001 0.040 T4 0.035 0.001 0.010 T6 0.046 0.001 0.040
Gravity die casting F 0.032 0.001 0.040 AM60 Die casting F 0.021
0.003 0.010 AM50 Die casting F 0.015 0.003 0.010 AS41 Die casting F
0.010 0.004 0.020 AE42 Die casting F 0.020 0.020 0.100
[0015] It has been found that these tolerance definitions are not
sufficient to reliably exclude the formation of corrosion-promoting
intermetallic phases, which in terms of electrochemistry have a
more noble potential than the magnesium matrix.
[0016] Biodegradable implants require a load-bearing function and
consequently strength, together with sufficient expandability,
during the physiologically necessary support periods thereof. Known
magnesium materials fall far short of the strength properties
provided by permanent implants made from other materials such as
titanium, CoCr alloys and titanium alloys. The ultimate tensile
strength R.sub.m for permanent implants is approximately 500 MPa to
>1000 MPa, while that of magnesium materials is <275 MPa so
far, and in most cases <250 MPa.
[0017] Another drawback of many prior magnesium materials is that
the difference between ultimate tensile strength R.sub.m and proof
stress R.sub.p is small. In the case of implants that allow plastic
deformation, such as cardiovascular stents, this means that no
further resistance exists against deformation after initial
deformation of the material, and the regions that have already been
deformed are deformed further without any load increase. This can
lead to overstretching of parts of the component and fracture may
occur.
[0018] Many magnesium materials additionally exhibit a clearly
pronounced mechanical asymmetry, which is manifested in the
difference in the mechanical properties, especially the proof
stress R.sub.p with tension load and compression load. Such
asymmetries are created, for example, during forming processes such
as extrusion, rolling and drawing, which are used to produce
suitable semi-finished products. A difference between the proof
stress R.sub.p during tension and the proof stress R.sub.p during
compression that is too large may result in inhomogeneous
deformation of a component, such as a cardiovascular stent, which
later undergoes multiaxial deformation, and may cause cracking and
fracture.
[0019] Because of the low number of crystallographic slip systems,
magnesium alloys can generally also form textures during forming
processes such as extrusion, rolling and drawing used to produce
suitable semifinished products by orienting the grains during the
forming process. Specifically, this means that the semifinished
product has different properties in different directions in space.
For example, high deformability or elongation at fracture occurs in
one direction in space after forming, and reduced deformability or
elongation at fracture occurs in another direction in space. The
formation of such textures should likewise be avoided, because a
stent is subjected to high plastic deformation, and reduced
elongation at fracture increases the risk of failure of the
implant. One method for substantially avoiding such textures during
forming is to adjust as fine a grain as possible prior to forming.
Because of the hexagonal lattice structure of magnesium materials,
the ability of these materials to deform at room temperature is
low, which is characterized by slip in the base plane. If the
material additionally has a coarse microstructure, i.e., a coarse
grain, so-called twinning is forcibly produced upon further
deformation, at which shear strain occurs, which transforms a
crystal region into a position that is mirror symmetrical to the
starting position. The resulting twin grain boundaries constitute
weak points in the material, where incipient cracking starts,
especially with plastic deformation, which ultimately leads to the
destruction of the component.
[0020] If the grain of the implant materials is sufficiently fine,
the risk of such implant failure is drastically reduced. Implant
materials should therefore have as fine a grain as possible so as
to prevent such undesirable shear strain.
[0021] All available magnesium materials for implants are subject
to high corrosion in physiological media. Attempts have been made
to curb the corrosion tendency by providing the implants with a
corrosion-inhibiting coating, for example made of polymeric
materials (EP 2 085 100 A2, EP 2 384 725 A1), an aqueous or
alcoholic conversion solution (DE 10 2006 060 501 A1) or an oxide
(DE 10 2010 027 532 A1, EP 0 295 397 A1).
[0022] The polymeric passivation layers are controversial, because
virtually all appropriate polymers also cause strong inflammations
in the tissue at times. On the other hand, thin magnesium alloy
structures without such protective measures do not resist
corrosions for the required support periods. The corrosion on
thin-walled traumatological implants is often times accompanied by
an excessively fast loss of tensile strength, which poses an
additional burden by forming excessive amounts of hydrogen per unit
of time. The consequences are undesirable gas inclusions in the
bones and tissue. In the case of traumatological implants having
larger cross-sections, there is a need to be able to deliberately
control the hydrogen problem and the corrosion rate of the implant
by way of the structure thereof.
[0023] Specifically with biodegradable implants, there is a desire
for maximum biocompatibility of the elements, because all the
chemical elements that are contained are absorbed by the body after
decomposition. In any case, highly toxic elements such as Be, Cd,
Pb, Cr and the like should be avoided.
[0024] Degradable magnesium alloys are especially suitable for
implementing implants which have been employed in a wide variety of
forms in modern medical technology. Implants are used, for example,
to support vessels, hollow organs and vein systems (endovascular
implants, such as stents), for fastening and temporarily fixing
tissue implants and tissue transplantations, but also for
orthopedic purposes, such as nails, plates or screws. A
particularly frequently used form of an implant is the stent.
[0025] The implantation of stents has become established as one of
the most effective therapeutic measures for the treatment of
vascular diseases. Stents have the purpose of assuming a supporting
function in hollow organs of a patient. For this purpose, stents
featuring conventional designs have a filigree supporting structure
comprising metal struts, which is initially present in compressed
form for introduction into the body and is expanded at the site of
the application. One of the main application areas of such stents
is to permanently or temporarily widen and hold open vascular
constrictions, particularly constrictions (stenosis) of coronary
blood vessels. In addition, aneurysm stents are known, which are
used primarily to seal the aneurysm. The support function is
additionally provided.
[0026] A stent has a base body made of an implant material. An
implant material is a non-living material, which is employed for
applications in medicine and interacts with biological systems. A
basic prerequisite for the use of a material as an implant
material, which is in contact with the body environment when used
as intended, is biocompatibility. For the purpose of the present
application, biocompatibility shall be understood to mean the
ability of a material to induce an appropriate tissue reaction in a
specific application. This includes an adaptation of the chemical,
physical, biological, and morphological surface properties of an
implant to the recipient's tissue with the aim of a clinically
desired interaction. The biocompatibility of the implant material
is also dependent on the temporal process of the reaction of the
biosystem in which it is implanted. For example, irritations and
inflammations occur in a relatively short time, which can lead to
tissue changes. Depending on the properties of the implant
material, biological systems thus react in different ways.
According to the reaction of the biosystem, the implant materials
can be divided into bioactive, bioinert and degradable or
resorbable materials.
[0027] Conventional implant materials include polymers, metallic
materials, and ceramic materials (as coatings, for example).
Biocompatible metals and metal alloys for permanent implants
include, for example, stainless steels (such as 316L), cobalt-based
alloys (such as CoCrMo cast alloys, CoCrMo forge alloys, CoCrWNi
forge alloys and CoCrNiMo forge alloys), pure titanium and titanium
alloys (such as cp titanium, TiAl6V4 or TiAl6Nb7) and gold alloys.
In the field of biocorrodible stents, the use of magnesium or pure
iron as well as biocorrodible base alloys of the elements
magnesium, iron, zinc, molybdenum, and tungsten have been
proposed.
[0028] The use of biocorrodible magnesium alloys for temporary
implants having filigree structures is made difficult in particular
because degradation of the implant progresses very quickly in vivo.
So as to reduce the corrosion rate, i.e., the degradation speed,
different approaches are being discussed in the art. Modified
alloys and coatings represent categories of approaches to reduce
the corrosion rate of magnesium alloys. Some of the existing
approaches show promise, but none of them has so far led to a
commercially available product to the knowledge of the inventors.
Regardless of the efforts made so far, there remains a need for
solutions to at least temporarily reduce the corrosion of magnesium
alloys in vivo, while optimizing the mechanical properties thereof
at the same time.
SUMMARY OF THE INVENTION
[0029] Preferred embodiments of the invention provide a
biodegradable magnesium alloy, a method for the production thereof
and implants made from the alloy, which allow the magnesium matrix
of the implant to remain in an electrochemically stable state over
the required support period with fine grain and high corrosion
resistance without protective layers, and to utilize the formation
of intermetallic phases, which electrochemically are more noble
than the magnesium matrix, while also improving the mechanical
properties, such as increasing the tensile strength and proof
stress, as well as reducing the mechanical asymmetry so as to
adjust the degradation rate of the implants.
[0030] A preferred magnesium alloy includes less or equal to 4.0%
by weight Zn, 2.0 to 10.0% by weight Al, wherein the alloy content
of Al in % by weight is greater than or equal to the alloy content
of Zn in % by weight, with the remainder being magnesium which
contains impurities, which promote electrochemical potential
differences and/or the formation of precipitations and/or
intermetallic phases, in a total amount of no more than 0.0063% by
weight of Fe, Si, Mn, Co, Ni, Cu, Zr, Y, Sc or rare earths having
the ordinal numbers 21, 57 to 71 and 89 to 103, Be, Cd, In, Sn
and/or Pb as well as P, wherein the matrix of the alloy is solid
solution hardening due to Al and Zn and is also particle hardening
due to the intermetallic phases formed of Mg and Al.
[0031] Preferably, the magnesium alloy has a content of Zn less or
equal 2.0% by weight, in particular preferably less or equal 1.0%
by weight and/or a content of Al in the range of 2.0 to 8.0% by
weight, preferably 3.0 to 8.0% by weight and still more preferably
3.0 to 6.0% by weight.
[0032] A preferred method of producing a magnesium alloy includes
generating a high-purity magnesium by vacuum distillation. A billet
of the alloy is synthesized with the high-purity magnesium and with
less or equal 4.0% by weight Zn, 2.0 to 10.0% by weight Al, wherein
the alloy content of Al in % by weight is greater than or equal to
the alloy content of Zn in % by weight, the remainder being
magnesium containing impurities, which promote electrochemical
potential differences and/or the formation of precipitations and/or
intermetallic phases, in a total amount of no more than 0.0063% by
weight of Fe, Si, Mn, Co, Ni, Cu, Zr, Y, Sc or rare earths having
the ordinal numbers 21, 57 to 71 and 89 to 103, Be, Cd, In, Sn
and/or Pb as well as P, wherein the matrix of the alloy is solid
solution hardening due to Al and Zn and is also particle hardening
due to the intermetallic phases formed of Mg and Al. The alloy is
homogenized by annealing at a temperature between 150.degree. C.
and 450.degree. C. with a holding period of 4 to 40 hours. The
homogenized alloy is formed in the temperature range between
200.degree. C. and 400.degree. C.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] The magnesium alloy according to the invention has very high
corrosion resistance, which is achieved by drastically reducing the
content of impurities and the combinations thereof in the magnesium
matrix, and by having only those alloying elements present which
raise the electrochemical potential of the matrix such that the
corrosion resistance of the alloy is considerably increased.
Corrosion resistance and deformability of the magnesium matrix of
an implant with an alloy of the invention can be assured over a
support period such that the implant is able to absorb multiaxial
permanent load without fracture or cracking, and the implant can
also benefit from the magnesium matrix for decomposition triggered
by the physiological liquids.
[0034] The previously known tolerance limits for impurities do not
take into account that wrought magnesium alloys often times are
subjected to a thermomechanical treatment, and more particularly to
an extended annealing process, which creates the near-equilibrium
structures. The metallic elements bond by way of diffusion and form
what are known as intermetallic phases, which have a different
electrochemical potential, notably a considerably higher potential,
than the magnesium matrix, and therefore these intermetallic phases
act as cathodes and can trigger galvanic corrosion processes.
[0035] The applicant has found that a corrosion-stable alloy matrix
can be achieved when complying with the following tolerance limits
of individual impurities in % by weight: Fe, Si, Mn, Co, Ni, Cu
each with <0.0005; Zr, Y each with <0.0003; and P<0.0002.
Further preferred in this embodiment, the alloy has additional
individual impurities in the following tolerance limits (% by
weight): Sc or rare earths having the ordinal numbers 21, 57 to 71
and 89 to 103 in total <0.001; Be, Cd, In, Sn and/or Pb each
with <0.0003.
[0036] Preferably, the corrosion-staple alloy matrix contains
impurities in a total amount of no more than 0.0053 Gew. %, which
can be achieved when complying with the following tolerance limits
of individual impurities in % by weight:
[0037] Fe, Si, Mn each with <0.0005; Co, Ni, Cu each with
<0.0002; Zr, Y each with <0.0003; Sc or rare earths having
the ordinal numbers 21, 57 to 71 and 89 to 103 in total <0.001;
Be, Cd, In, Sn and/or Pb each with <0.0003; and P<0.0001.
[0038] In particular preferred embodiments, the corrosion-staple
alloy matrix contains impurities in a total amount of no more than
0.0022 Gew.%, which can be achieved when complying with the
following tolerance limits of individual impurities in % by
weight:n: Fe, Si, Mn each with <0.0002; Co, Ni, Cu, Zr, Y each
with <0.0001; Sc or rare earths having the ordinal numbers 21,
57 to 71 and 89 to 103 in total <0.0005; Be, Cd, In, Sn and/or
Pb each with <0.0001, and P<0.0001.
[0039] It is surprising that the addition of manganese as an
alloying element, which is customary in the prior art, can be
dispensed with when these tolerance limits are adhered. The
formation of the ternary intermetallic phase FeMnSi is suppressed,
whereby the corrosion resistance of the alloy is improved.
[0040] When the impurity elements are combined, this tolerance
limit of the sum of impurities of Fe, Si, Mn, Co, Ni and Cu is no
more than 0.003% by weight, preferably no more than 0.0021% by
weight and in particular preferred no more than 0.0009% by
weight.
[0041] Preferred magnesium alloys according to the present
invention can achieve a tensile strength of >275 MPa, and
preferably >300 MPa, a yield point of >200 MPa, and
preferably >225 MPa, and a yield ratio of <0.8, and
preferably <075, wherein the difference between the tensile
strength and yield point is >50 MPa, and preferably >100 MPa,
and the mechanical asymmetry is <1.25.
[0042] These significantly improved mechanical properties can be
attributed to the formation of solid solutions between aluminum and
zinc in the alloy matrix as well as to the intermetallic phases of
magnesium and aluminum occurring in the matrix. The basis for the
increased tensile strength is the interaction of the dislocations
with the particles, whereby the dislocation movement is adversely
impacted and additional tension is required in order to generate
the same plastic deformation as in an undisturbed matrix.
[0043] The improved mechanical properties of the novel magnesium
alloys assure that the implants, for example cardiovascular stents,
are able to withstand the multiaxial permanent load in the
implanted state over the entire support period, despite onsetting
degradation of the magnesium matrix due to corrosion.
[0044] For the mechanical asymmetry, it is particularly important
for the magnesium alloy to have a particularly fine microstructure
having a grain size of no more than 7.5 .mu.m, preferably <5
.mu.m, and still more preferably <2.5 .mu.m.
[0045] A preferred method for producing a magnesium alloy having
the improved mechanical and electrochemical properties is also
provided by the invention. The method comprises the following
steps: [0046] a) generating high-purity magnesium by vacuum
distillation; [0047] b) generating a billet of the alloy by
synthesis of the magnesium according to step a) with less or equal
4.0% by weight Zn, 2.0 to 10.0% by weight Al, wherein the alloy
content of Al in % by weight is greater than or equal to the alloy
content of Zn in % by weight, the remainder being magnesium
containing impurities, which promote electrochemical potential
differences and/or the formation of precipitations and/or
intermetallic phases, in a total amount of no more than 0.0063% by
weight of Fe, Si, Mn, Co, Ni, Cu, Zr, Y, Sc or rare earths having
the ordinal numbers 21, 57 to 71 and 89 to 103, Be, Cd, In, Sn
and/or Pb as well as P, wherein the matrix of the alloy is solid
solution hardening due to Al and Zn and is also particle hardening
due to the intermetallic phases formed of Mg and Al; [0048] c)
homogenizing the alloy by annealing at a temperature between
150.degree. C. and 450.degree. C. with a holding period of 4 to 40
hours; and [0049] d) forming the homogenized alloy in the
temperature range between 200.degree. C. and 400.degree. C.
[0050] Preferably steps c) and d) can be repeated at least
once.
[0051] After step c) and before step d) an ageing treatment step
can be performed. Depending on the alloy composition and/or the
amount and/or type of the grains and/or the grain size ageing
treatment step can be performed at a temperature between 20.degree.
C. and 300.degree. C. with a holding period of 1 h to 168 h.
Preferably the ageing treatment can be performed at a temperature
between 20.degree. C. and 275.degree. C., still more preferably at
a temperature of 150.degree. C. with a holding period of 120
hours.
[0052] In a preferred value range steps c) is performed at a
temperature between 250.degree. C. and 450.degree. C. and/or step
d) is performed at a temperature between 225.degree. C. and
400.degree. C.
[0053] Preferably, the magnesium alloy generated by step a) has a
content of Zn less or equal 2.0% by weight, in particular
preferably less or equal 1.0% by weight and/or a content of Al in
the range of 2.0 to 8.0% by weight, preferably 3.0 to 8.0% by
weight and still more preferably 3.0 to 6.0% by weight.
[0054] Vacuum distillation is preferably used to produce a starting
material for a high-purity magnesium-aluminum-zinc alloy having the
required threshold values.
[0055] The sum of impurities can be selectively adjusted and in %
by weight are: [0056] a) for the individual impurities: [0057] Fe,
Si, Mn, Co, Ni, Cu each with <0.0005; [0058] Zr, Y each with
<0.0003; and [0059] P<0.0002. [0060] Preferably in this
embodiment additional individual impurities in the following
tolerance limits (% by weight): [0061] Sc or rare earths having the
ordinal numbers 21, 57 to 71 and 89 to 103 in total <0.001; Be,
Cd, In, Sn and/or Pb each with <0.0003. [0062] aa) for the
individual impurities in a preferred total amount of impurities of
no more than 0.0053% by weight: [0063] Fe, Si, Mn each with
<0.0005; [0064] Co, Ni, Cu each with <0.0002; [0065] Zr, Y
each with <0.0003; [0066] Sc or rare earths having the ordinal
numbers 21, 57 to 71 and 89 to 103 in total <0.001; [0067] Be,
Cd, In, Sn and/or Pb each with <0.0003; and [0068] P<0.0001.
[0069] ab) for the individual impurities in a particularly
preferred total amount of impurities of no more than 0.0022% by
weight: [0070] Fe, Si, Mn each with <0.0002; [0071] Co, Ni, Cu,
Zr, Y each with <0.0001; [0072] Sc or rare earths having the
ordinal numbers 21, 57 to 71 and 89 to 103 in total <0.0005;
[0073] Be, Cd, In, Sn and/or Pb each with <0.0001; and [0074]
P<0.0001. [0075] b) for the combination of individual impurities
in total: [0076] Fe, Si, Mn, Co, Ni, Cu no more than 0.003,
preferably no more than 0.0021% by weight and in particular
preferred no more than 0.0009% by weight.
[0077] It is particularly advantageous that the preferred method
only requires a small number of forming steps. Extrusion, equal
channel angular extrusion and/or multiple forging can thus
preferably be employed, which assure that a substantially
homogeneous fine grain of <10 .mu.m is achieved.
[0078] The magnesium alloy produced according to the method, which
has the above described advantageous composition and structure, in
medical technology, can also be used in the production of implants,
for example endovascular implants such as stents, for fastening and
temporarily fixing tissue implants and tissue transplantations,
orthopedic and dental implants, and neuroimplants.
[0079] Particular implants of the invention are in the
Cardiovascular field, osteosynthesis field or other areas.
[0080] Cardiovascular field in the sense of this application
includes [0081] the field of diagnostic, prevention and treatment
of all diseases of the cardiovascular system, i.e. heart and blood
vessel system, [0082] by mean of active and non-active implants
used to support vessels, and vein systems [0083] including
coronary, cerebral and peripheral vascular implants like stents,
valves, closure devices, occluders, clips, coils, staples,
implantable regional drug delivery devices, [0084] implantable
electrostimulators (like pacemakers and defibrillators),
implantable monitoring devices, implantable electrodes, [0085]
system for fastening and temporarily fixing tissue implants and
tissue transplantations [0086] field also includes any type of
stent as mechanical fix or temporary scaffold to support hollow
organs and structures including bones, intervertebral disks
[0087] Osteosynthesis in the sense of this application includes
[0088] the field of treatment of fractured bones for internal
fixation and stabilization by mechanical devices such as metal
plates, pins, rods, wires, screws, clips, nails, staples excluding
stent technology
[0089] Examples of areas out of the osteosynthesis field or the
cardiovascular field are: [0090] Devices for the treatment of
diseases of the sinews, joints, muscles, cartilages, [0091] oral
(including dental) and maxillo facial implants (excl.
osteosynthesis means), [0092] esthetic implants, [0093] supporting
tools out of the body, [0094] tissue engineering, [0095] soft
tissue implants, [0096] devices for wound care, [0097] suture
material and clamps, [0098] neurosurgery [0099] local drug delivery
(excl. cardiovascular, i.e. lever) [0100] renal
Exemplary Embodiment 1
[0101] A magnesium alloy is generated which is composed of 2.0% by
weight Zn and 6.0% by weight Al, the remainder being Mg, and
contains the following individual impurities in % by weight:
Fe: <0.0005; Si: <0.0005; Mn: <0.0005; Co: <0.0002; Ni:
<0.0002; Cu<0.0002, wherein the sum of impurities of Fe, Si,
Mn, Co, Ni, Cu is no more than 0.0021% by weight and that of Zr is
no more than 0.0003% by weight.
[0102] The magnesium produced with aid of vacuum distillation is
melted with high-purity Al and Zn in a graphite crucible, and the
alloy is subjected to homogenizing annealing at a temperature of
360.degree. C. for a duration of 24 hours, and subsequently to
multiple extrusion processes at a temperature of 300.degree. C., so
as to produce a precision tube for a cardiovascular stent.
[0103] The grain size of the microstructure was <5.5 .mu.m, and
the particle size of the intermetallic phases dispersely
distributed in the alloy matrix was 0.5 .mu.m.
[0104] The magnesium alloy reached a tensile strength of 310 to 320
MPa and proof stress of approximately 250 MPa [sic]. The yield
ratio was 0.79 and the mechanical asymmetry was 1.2.
Exemplary Embodiment 2
[0105] A magnesium alloy is generated which is composed of 0.25% by
weight Zn and 2.50% by weight Al, the remainder being Mg, and
contains the following individual impurities in % by weight:
[0106] Fe: <0.0005; Si: <0.0005; Mn: <0.0005; Co:
<0.0002; Ni: <0.0002; Cu<0.0002, wherein the sum of
impurities of Fe, Si, Mn, Co, Ni, Cu is no more than 0.0021% by
weight and that of Zr is no more than 0.0003% by weight.
[0107] The magnesium produced with aid of vacuum distillation is
melted with high-purity Al and Zn in a graphite crucible, and the
alloy is subjected to homogenizing annealing at a temperature of
360.degree. C. for a duration of 24 hours, and subsequently to
multiple extrusion processes at a temperature of 300.degree. C., so
as to produce a precision tube for a cardiovascular stent.
[0108] The grain size of the microstructure was <5.5 .mu.m, and
the particle size of the intermetallic phases dispersely
distributed in the alloy matrix was 0.5 .mu.m.
[0109] The magnesium alloy reached a tensile strength of 310 to 320
MPa and proof stress of approximately 250 MPa [sic]. The yield
ratio was 0.79 and the mechanical asymmetry was 1.2.
Exemplary Embodiment 3
[0110] A magnesium alloy is generated which is composed of 5.0% by
weight Al, the remainder being Mg, and contains the following
individual impurities in % by weight:
[0111] Fe: <0.0005; Si: <0.0005; Mn: <0.0005; Co:
<0.0002; Ni: <0.0002; Cu<0.0002, wherein the sum of
impurities of Fe, Si, Mn, Co, Ni, Cu is no more than 0.0021% by
weight and that of Zr is no more than 0.0003% by weight.
[0112] The magnesium produced with aid of vacuum distillation is
melted with high-purity Al in a graphite crucible, and the alloy is
subjected to homogenizing annealing at a temperature of 360.degree.
C. for a duration of 24 hours, and subsequently to multiple
extrusion processes at a temperature of 300.degree. C., so as to
produce a precision tube for a cardiovascular stent.
[0113] The grain size of the microstructure was <5.5 .mu.m, and
the particle size of the intermetallic phases dispersely
distributed in the alloy matrix was 0.5 .mu.m.
[0114] The magnesium alloy reached a tensile strength of 310 to 320
MPa and proof stress of approximately 250 MPa [sic]. The yield
ratio was 0.79 and the mechanical asymmetry was 1.2.
Exemplary Embodiment 4
[0115] A magnesium alloy is generated which is composed of 3% by
weight Al, the remainder being Mg, and contains the following
individual impurities in % by weight:
[0116] Fe: <0.0005; Si: <0.0005; Mn: <0.0005; Co:
<0.0002; Ni: <0.0002; Cu<0.0002, wherein the sum of
impurities of Fe, Si, Mn, Co, Ni, Cu is no more than 0.0021% by
weight and that of Zr is no more than 0.0003% by weight.
[0117] The magnesium produced with aid of vacuum distillation is
melted with high-purity Al in a graphite crucible, and the alloy is
subjected to homogenizing annealing at a temperature of 360.degree.
C. for a duration of 24 hours, and subsequently to multiple
extrusion processes at a temperature of 300.degree. C., so as to
produce a precision tube for a cardiovascular stent.
[0118] The grain size of the microstructure was <5.5 .mu.m, and
the particle size of the intermetallic phases dispersely
distributed in the alloy matrix was 0.5 .mu.m.
[0119] The magnesium alloy reached a tensile strength of 310 to 320
MPa and proof stress of approximately 250 MPa [sic]. The yield
ratio was 0.79 and the mechanical asymmetry was 1.2.
Exemplary Embodiment 5
[0120] A magnesium alloy is generated which is composed of 0.25% by
weight Zn and 2.0% by weight Al, the remainder being Mg, and
contains the following individual impurities in % by weight:
[0121] Fe: <0.0005; Si: <0.0005; Mn: <0.0005; Co:
<0.0002; Ni: <0.0002; Cu<0.0002, wherein the sum of
impurities of Fe, Si, Mn, Co, Ni, Cu is no more than 0.0021% by
weight and that of Zr is no more than 0.0003% by weight.
[0122] The magnesium produced with aid of vacuum distillation is
melted with high-purity Al and Zn in a graphite crucible, and the
alloy is subjected to homogenizing annealing at a temperature of
360.degree. C. for a duration of 24 hours and thereafter to an
ageing treatment at 125.degree. C. for 120 hours.
[0123] Subsequently, the material is subjected to multiple
extrusion processes at a temperature of 200.degree. C., so as to
produce a precision tube for a cardiovascular stent.
[0124] Before the final extrusion step is applied another annealing
process is performed at 150.degree. C. for 3 hours.
[0125] The grain size of the microstructure was <5.5 .mu.m, and
the particle size of the intermetallic phases dispersely
distributed in the alloy matrix was 0.5 .mu.m.
[0126] The magnesium alloy reached a tensile strength of 320 to 350
MPa and proof stress of approximately 235 MPa. The yield ratio was
0.70 and the mechanical asymmetry was 1.2.
Exemplary Embodiment 6
[0127] A magnesium alloy is generated which is composed of 1.5% by
weight Zn and 3.0% by weight Al, the remainder being Mg, and
contains the following individual impurities in % by weight:
[0128] Fe: <0.0005; Si: <0.0005; Mn: <0.0005; Co:
<0.0002; Ni: <0.0002; Cu<0.0002, wherein the sum of
impurities of Fe, Si, Mn, Co, Ni, Cu is no more than 0.0021% by
weight and that of Zr is no more than 0.0003% by weight.
[0129] The magnesium produced with aid of vacuum distillation is
melted with high-purity Al and Zn in a graphite crucible, and the
alloy is subjected to homogenizing annealing at a temperature of
360.degree. C. for a duration of 24 hours and thereafter to an
ageing treatment at 150.degree. C. for 120 hours.
[0130] Subsequently, the material is subjected to an extrusion
process at a temperature of 200.degree. C., so as to produce a rod
with 8 mm diameter to produce screws for craniofacial
fixations.
[0131] The grain size of the microstructure was <3.0 .mu.m, and
the particle size of the intermetallic phases dispersely
distributed in the alloy matrix was 0.5 .mu.m.
[0132] The magnesium alloy reached a tensile strength of 340 to 360
MPa and proof stress of approximately 250 MPa [sic]. The yield
ratio was 0.71 and the mechanical asymmetry was 1.2.
[0133] While specific embodiments of the present invention have
been shown and described, it should be understood that other
modifications, substitutions and alternatives are apparent to one
of ordinary skill in the art. Such modifications, substitutions and
alternatives can be made without departing from the spirit and
scope of the invention, which should be determined from the
appended claims.
[0134] Various features of the invention are set forth in the
appended claims.
* * * * *