USOO7357854B1

(12) United States Patent (10) Patent No.: US 7,357,854 B1

Andreacchi (45) Date of Patent: Apr. 15, 2008
(54) PROCESS FOR ELECTROPOLISHING A 6,019,784. A 2/2000 Hines
DEVICE MADE FROM 6,131,266 A 10/2000 Saunders
COBALT-CHROMIUM 6,334,871 B1 1/2002 Dor et al.
6,355,058 B1 3/2002 Pacetti et al.
(75) Inventor: Anthony S. Andreacchi, San Jose, CA (Continued)
FOREIGN PATENT DOCUMENTS
(73) Assignee: tled arly Systems, JP 56152999 A * 11, 1981
(Continued)
(*) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 OTHER PUBLICATIONS
U.S.C. 154(b) by 938 days. Standard Guide for Electrolytic Polishing of Metallographic Speci
mens, American Society and Materials (Designation: E 1558-93),
(21) Appl. No.: 10/223,273 pp. 1-12, 1993, ..
(22) Filed: Aug. 19, 2002 (Continued)
Primary Examiner SuSV Tsang-Foster
(51) Int. Cl. y y Sang
C25F 3/6 (2006.01) Assistant Examiner Nicholas A. Smith
(52) U.S. Cl 205,674. 205/640: 205/682: (74) Attorney, Agent, or Firm Fulwider Patton LLP
205/684; 205/723 (57) ABSTRACT
(58) Field of Classification Search ........ 205/640–686,
205/723 The invention is directed to an electropolishing solution for
See application file for complete search history. products or devices made from at least in part a cobalt
(56) References Cited chromium alloy. The invention is particularly suitable for
medical devices or intravascular stents made at least in part
U.S. PATENT DOCUMENTS of cobalt-chromium. More particularly, the electropolishing
2,645,611 A 7, 1953 Axtell ........................ 205,671
process of the invention is particularly Suited for use on
2,674,571 A * 4, 1954 Prosen ....................... 205,678 implantable medical devices, such as Stents, due to the
3,556,883. A 1/1971 Naito et al. biocompatibility of cobalt-chromium alloys. The invention
3,986,970 A 10/1976 Shiga is directed to an improved stent formed from a cobalt
4.425.204 A * 1/1984 McLaughlin ................ 205,671 chromium alloy, that possesses an ultrasmooth shiny Sur
5,158,548 A 10, 1992 Lau et al. face. This invention is also directed to a method of elec
5,344.425. A 9/1994 Sawyer tropolishing such a stent using an acidic electrolytic Solution
5,421.955 A 6, 1995 Lau et al. comprising a mixture of 6 parts of about 98% sulfuric acid
5.449,372 A 9, 1995 Schmaltz et al. (HSO), 1 part of about 37% hydrochloric acid (HCl) and
5,514,154 A 5, 1996 Lau et al. 1 part by of about 85% concentrated phosphoric acid
5,679,470 A 10/1997 Mayer (HPO) to produce an exceptionally smooth surface.
5,750,434 A 5, 1998 Urushidani et al.
5,824,077 A 10/1998 Mayer
5,891,191 A 4/1999 Stinson 16 Claims, 3 Drawing Sheets

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XX.
 US 7,357,854 B1
Page 2

U.S. PATENT DOCUMENTS Surman, Hartmut et al., Automatic Electropolishing of Cobalt

Chromium Dental Cast Alloys With A Fuzzy Logic Controller,
6,465,124 B1 * 10/2002 Medeiros et al. ........... 429,105 Computers Chemical Engineering, vol. 22, No. 7-8, pp. 1099-1111.
6,736,952 B2 * 5/2004 Emesh et al. ..... ... 20581 1998, n. m.
6,916.409 B1* 7/2005 Callol et al. ........... 204/297.05 ESMA, Inc. Brochure re electropolishers; Mar. 2002.
Standard Guide for Electrolytic Polishing of Metallographic Speci
FOREIGN PATENT DOCUMENTS mens, American Society and Materials (Designation: E 1558-93),
pp. 1-12, 1993.
JP 4O9207029 A * 8, 1997 Standard Practice for Microetching Metals and Alloys, American
Society and Materials (Designation: E 407-93), pp. 1-18, 1993.
OTHER PUBLICATIONS Standard Test Method for Macroetching Metals and Alloys, Ameri
can Society and Materials (Designation: E 340-93), pp. 1-10, 1993.
Standard Practice for Microetching Metals and Alloys, American Surman, Hartmut et al., Automatic Electropolishing of Cobalt
Society and Materials (Designation: E 407-93), pp. 1-18, 1993, n.m. Chromium Dental Cast Alloys With a Fuzzy Logic Controller,
Standard Test Method for Macroetching Metals and Alloys, Ameri Computers Chemical Engineering, vol. 22, No. 7-8, pp. 1099-1111.
1998.
can Society and Materials (Designation: E 340-93), pp. 1-10, 1993,
.. * cited by examiner
U.S. Patent Apr. 15, 2008 Sheet 2 of 3 US 7,357,854 B1
U.S. Patent Apr. 15, 2008 Sheet 3 of 3 US 7,357,854 B1
 US 7,357,854 B1
1. 2
PROCESS FOR ELECTROPOLISHING A for stent construction. Stainless steel is corrosion resistant,
DEVICE MADE FROM strong, yet may be cut into very thin walled stent patterns.
COBALTCHROMIUM Cobalt-chromium alloy is a metal that has proven advan
tages when used in stent applications. Stents made from
BACKGROUND OF THE INVENTION cobalt-chromium alloy may be thinner and lighter in weight
than stents made from other metallic materials, including
The invention relates generally to providing an electro stainless steel. Cobalt-chromium alloy is also a denser metal
lytic acid solution for electropolishing products made from than stainless steel. Additionally, cobalt-chromium stents are
cobalt-chromium alloys. More particularly, the invention nontranslucent to certain electromagnetic radiation waves,
relates to electropolishing medical devices made of cobalt 10 Such as X rays, and, relative to stainless Steel stents, provide
chromium alloys, and even more particularly, the invention a higher degree of radiopacity, thus being easier to identify
relates to electrolytic acid solutions used to Smoothly elec in the body under fluoroscopy.
tropolish stents formed from cobalt-chromium alloy. This Metal stents, however, suffer from a number disadvan
invention includes the solutions, the method of electropol tages. They often require processing to eliminate undesir
ishing a cobalt-chromium stent using the solutions, and a 15 able burrs, nicks, or sharp ends. Expandable metal stents are
cobalt-chromium stent having an outer Surface electropol frequently formed by use of a laser to cut a framework
ished with the solutions. design from a tube of metal. The tubular stent wall is formed
While a wide range of products or devices can be made into a lattice arrangement consisting of metal struts with
from a cobalt-chromium alloy for use with the present gaps therebetween. Laser cutting, however, typically is at
invention, medical devices are particularly suitable due to high temperature and often leaves debris and slag material
the biocompatible characteristics of cobalt-chromium prod attached to the stent. Such material, if left on a stent, would
ucts. Thus, for example, implantable medical devices or render the stent unacceptable for implantation. Treatment to
devices that are used within the human body are particularly remove the slag, burrs, and nicks is therefore required to
suitable and can be made from a cobalt-chromium alloy that provide a device suitable for use in a body lumen.
has been electropolished in accordance with the present 25 Descaling is typically a first treatment of the Surface in
invention. More particularly, and as described in more detail preparation for further surface treatment such as electropol
herein, intravascular stents can be made from a cobalt ishing. Descaling may include, for example, Scraping the
chromium alloy that has been electropolished according to stent with a diamond file, followed by dipping the stent in
the invention. Thus, while the description of prior art devices 30 hydrochloric acid or a hydrochloric acid mixture, and there
and of the invention herein refers mainly to intravascular after cleaning the stent ultrasonically. A Successfully des
stents, the invention is not so limited. caled metal stent should be substantially slag-free in prepa
Stents are generally metallic tube shaped intravascular ration for subsequent electropolishing.
devices which are placed within a blood vessel to structur technique finishing
Further is often accomplished by the well known
ally hold open the vessel. The device can be used to maintain 35 bling techniques are often notGrinding,
of electropolishing.
Suited
vibration, and tum
to be employed on
the patency of a blood vessel immediately after intravascular Small detailed parts such as stents.
treatments and can be used to reduce the likelihood of
development of restenosis. Expandable stents are frequently Prior art electropolishing methods generally improve the
Smoothness
used as they may travel in compressed form to the Stenotic chromium stents of the metal Surface, but as applied to cobalt
site generally either crimped onto an inflation balloon or 0 produce a desirablyhave had been limited in the ability to
consistent Smooth surface.
compressed into a containment sheath in a known manner. Electropolishing is an electrochemical process by which
Expandable stents formed from metal offer a number of surface metal is dissolved. Sometimes referred to as “reverse
advantages and are widely used. Metallic serpentine Stents, plating, the electropolishing process actually removes
for example, not only provide strength and rigidity once metal from the surface desired to be smoothed. The metal
implanted they also are designed sufficiently compressible 45 stent is connected to a power Supply (the anode) and is
and flexible for traveling through the tortuous pathways of immersed in a liquid electrolytic Solution along with a metal
the vessel route prior to arrival at the stenotic site. Addi cathode connected to the negative terminal of the power
tionally, metallic stents may be radiopaque, thus easily Supply. Current is applied and flows from the stent, causing
visible by radiation illumination techniques such as X-ray it to become polarized. The applied current is controlled to
film. 50 control the rate at which the metal ions of the anodic stent
It is highly desirable for the surface of the stent to be are generally removed and diffused through the Solution to
extremely smooth so that it can be inserted easily and the cathode.
experience low-friction travel through the tortuous vessel The rate of the electrochemical reaction is proportional to
pathway prior to implantation. A roughened outer Surface the current density. The positioning and thickness of the
may result in increased frictional obstruction during inser 55 cathode in relation to the stent is important to make available
tion and excess drag during travel to the Stenotic site as well an even distribution of current to the desired portion of the
as damaging the endothelium lining the vessel wall. A rough stent sought to be Smoothed.
Surface may cause frictional resistance to Such an extent as The straightforward application of current, however, does
to prevent travel to desired distal locations. A rough finish not necessarily translate to even distribution of current
may also cause damage to the underlying inflation balloon. 60 across the entire Surface sought to be polished. One impor
Aless rough finish decreases thrombogenicity and increases tant feature to creating an even Surface on the desired portion
corrosion resistance. of the part is the formation of current differential during the
Stents have been formed from various metals including electropolishing process across the Surface. Electropolishing
stainless steel, tantalum, titanium, platinum, nickel-titanium provides varied current density to the surface imperfections
which is commonly called nitinol, and alloys formed with 65 Such as undulations creating protrusions and Valleys on the
cobalt and chromium. Stainless steel has been extensively Surface. Current density is highest at high points on the
used to form stents and has often been the material of choice surface and lowest at the low points. The increased current
 US 7,357,854 B1
3 4
density at the raised points causes the metal to dissolve faster Such as medical implants, hip joints, bone screws, guide
at these points thus leveling the Surface while forming a wires, catheters, filters, and intravascular stents. Other prod
corrosion-inhibiting oxide layer. ucts and devices unrelated to the medical device products
Electropolishing in the proper electrolytic solution, can described herein also will benefit from the electropolishing
serve to Smooth out the exposed rough surface to the point Solution and process when Such products or devices are
where it is ultrasmooth, shiny, and reflective. However, made from cobalt-chromium alloys. Since the electropol
traditional methods have not proved effective to consistently ishing process of the invention is particularly useful for
produce an ultrasmooth, Shiny finish on a stent comprised of medical devices and more particularly useful for intravas
cobalt-chromium alloy. cular stents, the process is described herein with respect to
Treated with traditional electrolytic or etching solutions, 10 stents, but is not so limited.
such as those specified in ASTM E407-93, ASTM E340-95, The invention is directed to an improved product or
and ASTM E1558-93, a stent formed of cobalt-chromium device. Such as a stent, formed from a cobalt-chromium
alloy may reveal a variety of finishes ranging from a rather alloy, that possesses an ultrasmooth, shiny exterior Surface.
rough and unfinished appearance, a matte finish which is This invention is also directed to a method of electropol
pitted, brown, blackened, feathered, etched, dimpled, rough, 15 ishing Such a stent using an acidic electrolytic Solution
and/or uneven. comprising a mixture of about 6 parts of about 98% con
One prior art electropolishing Solution, comprising about centrated sulfuric acid (HSO), about 1 part of about 37%
3 parts by volume of about 98% concentrated sulfuric acid concentrated hydrochloric acid (HCl), and about 1 part of
and 1 part by volume of about 37% hydrochloric acid 85% concentrated phosphoric acid (HPO) (hereinafter
(hereinafter referred to as the "3:1 solution), provided an referred to as the “6:1:1 solution') to produce an exception
improved surface finish for cobalt-chromium stents. A suit ally Smooth surface. In another embodiment, the Solution
able overall treatment for a cobalt-chromium stent using the comprises a mixture of about 6 parts of about 98% concen
3:1 prior art electropolishing Solution includes initial des trated sulfuric acid (HSO) and about 1 part of 85%
caling wherein the stents are dipped in a hydrochloric acid concentrated phosphoric acid (HPO) to produce an excep
Solution and thereafter ultrasonically cleaned, electropolish 25 tionally smooth Surface. In yet another embodiment, the
ing using the prior art 3:1 solution and then some final acidic electrolytic solution comprises about 1 part by Vol
electropolishing using a mildly acidic solution. The above ume of a first component selected from the group consisting
treatment produces an acceptable Surface finish for a cobalt of ethylene glycol, ethylene glycol derivatives and mixtures
chromium stent having a tubular wall with a wall thickness, thereof and at least about 2 parts by volume of a second
before surface treatment, of about 0.005 inch. However, it 30 component that is an acid (hereinafter referred to as the
has a tendency to produce an uneven, pitted Surface on “ethylene glycol Solution') to produce a Smooth and shiny
cobalt-chromium stents having a tubular wall with a wall surface. More particularly, solutions of this embodiment
thickness, before surface treatment, of about 0.004 inch. may comprise about 1 part by Volume of the first component
Heretofore, there has been no effective method to consis that is a mixture of about equal parts by volume of ethylene
tently produce an ultrasmooth, shiny finish on the Surface of 35 glycol, ethylene glycol bisthioglycolate and ethylene glycol
a cobalt-chromium stent with a wall thickness, before sur diacetate and either about 3 parts by volume of the second
face treatment, of about 0.004 inch. component that is about 98% concentrated sulfuric acid or
It would be desirable to provide an electropolishing about 6 parts by Volume of the second component that is a
solution which would acceptably polish stents with wall mixture of about 5 parts by volume of 98% concentrated
thicknesses of 0.004 inch as well as up to 0.005 inch. A stent 40 sulfuric acid and about 1 part by volume of 37% hydrochlo
having a 0.004 inch thick tubular wall may be preferable ric acid or 85% phosphoric acid.
when smaller final dimensions for wall thickness are Compared to stainless steel, cobalt-chromium alloy pro
desired. Also, a stent having a 0.004 inch thick tubular wall vides a strong, flexible, lower weight and higher density
will generally have a shorter process time and more unifor stent. Cobalt-chromium alloy also provides a greater degree
mity across the length of the stent. 45 of radiopacity than stainless steel, a very desirable property
It would also be desirable to provide an electropolishing when seeking to locate the stent and when attempting to
Solution that could acceptably polish a cobalt-chromium observe its performance once implanted in a vessel. Such as
stent without an initial descaling treatment or without final a peripheral vessel or coronary artery.
electropolishing using a different solution in order to reduce The ability to consistently and adequately finish the
process time and the number of different solutions needed. 50 Surface of a cobalt-chromium stent has, however, been
Further, it would be desirable to provide an electropolishing limited. The improved method of finishing a stent comprised
solution with an increased threshold for both metal ion and of cobalt-chromium alloy herein disclosed provides an ultr
water contamination in order to reduce the frequency of asmooth, shiny, Stent Surface Suitable for low-friction inser
changing the Solution, thus further reducing process time tion and travel to the luminal location.
and costs. 55 In the present invention, to achieve an ultrasmooth, bright
What is needed is a process for treating a product or and shiny surface of a cobalt-chromium stent, the compo
device made of a cobalt-chromium alloy to consistently sition of the electrolytic solution is an important criteria. It
produce an ultrasmooth surface as well as to provide a more has been determined that one embodiment which achieves
simplified process, including a reduction in process time, the Such a result is comprised of a solution of about 6 parts of
number of Solutions needed and the frequency of replacing 60 about 98% concentrated sulfuric acid (HSO), about 1 part
the solution. The present invention satisfies these needs. of about 37% concentrated hydrochloric acid (HCl) and
about 1 part of 85% concentrated phosphoric acid (HPO).
SUMMARY OF THE INVENTION The solution may also include an ethylene glycol mixture as
a component. Another embodiment which achieves a
The invention is directed to a process of electropolishing 65 Smooth and shiny Surface is a solution comprising about 1
a product or device made from a cobalt-chromium alloy. The part by volume of a first component that is a mixture of about
product or device is particularly useful for medical devices equal parts by Volume of ethylene glycol, ethylene glycol
 US 7,357,854 B1
5 6
bisthioglycolate and ethylene glycol diacetate and either cobalt-chromium alloy, is electropolished in a solution of
about 3 parts by Volume of a second component that is about acid for a predetermined time and temperature in order to
98% concentrated sulfuric acid or about 6 parts by volume form an oxide coating on the product or device which
of a second component that is a mixture of about 5 parts by provides a Smooth and shiny Surface. In particular, the
volume of 98% concentrated sulfuric acid and about 1 part process of the invention is particularly suitable for medical
by volume of 37% hydrochloric acid or 85% phosphoric devices made of cobalt-chromium since cobalt-chromium is
acid. The concentration of acids may vary according to a a biocompatible metal alloy. More particularly, implantable
particular Smoothness requirement. The time that the cobalt devices such as intravascular stents, prosthetic devices, bone
chromium product or stent is exposed to the solution, the screws, and the like can be made from cobalt-chromium
temperature of the solution and the current (ranging from 10
alloys and be treated with the electropolishing solution of
about 1 amp to about 5 amps) also are factors that impact the the present invention. While the electropolishing solution of
surface finish of the cobalt-chromium stent or other product. the present invention can be used with any product or device
The 6:1:1 solution of the present invention consistently made at least in part from cobalt-chromium to produce a
produces a stent which has an ultrasmooth and shiny exterior Smooth and shiny Surface, the use of the invention for
Surface. Further, the solution produces ultraSmooth, Shiny 15
intravascular stents made from cobalt-chromium is particu
stents from hypotubes having a 0.004 inch thick tubular wall larly suitable and is described in much more detail herein.
in addition to hypotubes having a 0.005 inch thick tubular The invention is not limited to use with stents for medical
wall. The 6:1:1 solution more consistently produces an devices.
acceptably polished 0.004 inch thick stent compared to the
prior art 3:1 solution and provides a Smoother and shinier The improved cobalt-chromium stent is formed from an
surface finish overall than the prior art 3:1 solution on 0.004 alloy composed of cobalt and chromium comprising at least
inch thick stents. Compared to the prior art 3:1 electropol fifty percent by weight of the alloy and including one or
ishing Solution, the 6:1:1 Solution of the present invention is more of a variety of metals and elements as is known in the
also able to treat a cobalt-chromium stent in a shorter period art including, but not limited to nickel, titanium, tantalum,
of time. The 6:1:1 solution of the present invention is able 25 nickel-titanium, tungsten, manganese, molybdenum, Silicon,
to electropolish a stent in a fewer number of cycles and also carbon, and nitrogen. In one embodiment, an alloy of
eliminates the need for either an initial descaling treatment Co-Cr—W (cobalt-chromium-tungsten) was evaluated.
or additional electropolishing with a different, final solution, Cobalt-chromium Stents can be made from alloys known in
both of which were required by the prior art 3:1 solution. the art by the tradenames Haynes(R25, L605, and Stellite 25.
Furthermore, the 6:1:1 solution of the present invention is 30 Alternatively, the improved stent may be formed with an
able to withstand a greater water concentration and metalion exterior metal surface comprised of an alloy of cobalt and
chromium.
concentration before becoming ineffective to further polish
the stents. Typically, a cobalt-chromium stent incorporates a desired
The ethylene glycol solution of the present invention is lattice configuration usually laser cut from a tube of cobalt
also capable of producing a smooth and shiny stent. In 35 chromium alloy. During the laser cutting process, frequently
particular, the surface finish obtainable from electropolish much of the tube is cut away, to produce a chain of ring-like
ing a stent with the ethylene glycol Solution eliminates the elements comprised of struts in wave-like pattern with gaps
need for the final electropolishing solution. therebetween and links connecting the ring elements
Other features and advantages of the invention will together to form an elongated tubular body typically
become apparent from the following detailed description, 40 between 8 mm and 40 mm long. Implanted Stents have an
taken in conjunction with the accompanying drawings, internal diameter typically between 2 mm for small vessel
which illustrate, by way of example, the features of the stents and up to 8 mm for larger vessels. Crimpable or
invention. expandable stents in a compressed condition typically have
an internal diameter in the range of just under 1 mm to about
BRIEF DESCRIPTION OF THE DRAWINGS 45 2 mm. Before electropolishing or surface treatment, the
thickness of the stent wall is usually between 0.10 mm and
FIGS. 1 and 2 are schematic diagrams of an electropol 0.20 mm. All of these dimensions can vary to suit a
ishing fixture for use with the electropolishing procedure of particular application.
present invention. Such precision laser cutting, however, typically is at high
FIGS. 3A and 3B are photographs of the surface of a 50 temperature and often leaves debris and slag material
portion of a cobalt-chromium stent having a tubular wall attached to the stent requiring processing to eliminate it.
with a wall thickness, before surface treatment, of about Such debris and excess slag often exhibits itself in the form
0.004 inch electropolished with the 6:1:1 solution of the of undesirable bulges of material, burrs, nicks, and sharp
present invention. ends. The stent is typically descaled by dipping the stent in
FIGS. 4A and 4B are photographs of the surface of a 55 37% concentrated hydrochloric acid (HCl) or HCl solution
portion of a cobalt-chromium stent tube having a wall for approximately 5 minutes. Multiple stents may be so
thickness, before surface treatment, of about 0.004 inch dipped into a test tube of HC1. In one embodiment, the stent
electropolished with a prior art Solution consisting of about is immersed in a solution of about 9 parts of 37% concen
3 parts of about 98% concentrated sulfuric acid to 1 part of trated HCl to 1 part of 30% concentrated hydrogen peroxide
about 37% concentrated hydrochloric acid. 60 (HO) at room temperature. The HCl solution can be
repeatedly used until it turns dark green (from contami
DETAILED DESCRIPTION OF THE nants). Stents should be dipped slowly in the fresh HCl as
PREFERRED EMBODIMENTS the HC may react violently with them. In lieu of hydrochlo
ric acid, other acids may be used to descale the stent
The present invention is directed to an electropolishing 65 including nitric acid (HNO), phosphoric acid (HPO),
solution and product treated by that solution. More specifi sulfuric acid (HSO), or a combination of the above
cally, a product or device formed from at least in part a mentioned acids (i.e., HCl, HNO3, HPO and HSO).
 US 7,357,854 B1
7 8
The descaling procedure is thereafter completed by rins tubular member substantially surrounds the anode or metal
ing and drying the stent. The stent is ultrasonically rinsed in device. For example, the metallic device has a length and a
water, preferably distilled water at about 58° Celsius, for diameter such that the length and diameter of the tubular
about two minutes and then air dried. A procedure for member is greater than the length and diameter of the
preparing Such a stent for implantation includes descaling metallic device. As a more specific example, a typical
and electropolishing the stent. coronary stent 22 can range in length from approximately 6
If examination under a microscope reveals residual slag mm to 40 mm and have an unexpanded diameter in the range
the descaling process of acid bathing, ultrasonic rinsing, and of about 1.5 mm to 7 mm, depending upon the application.
drying should be repeated, although a stent can typically be In order to substantially surround the metal stent, the tubular
descaled in a single five minute cycle. A Successful descaling 10 member should have a length in the range of about 10 to 60
of the stent should yield slag-free stents in preparation for mm and a diameter in the range of about 4 to 70 mm.
Subsequent electropolishing. Should Small spots of slag Obviously, these dimensions for the metallic device and the
stubbornly cling to the stent, they can be electropolished tubular member can vary widely depending upon the appli
away without any adverse effects and without employing cation and the size of the metallic device being electropol
further descaling cycles to remove them. 15 ished. Further, the invention is not limited to electropolish
Descaling yields a roughened, but clean Surface available ing medical devices, rather it is useful for any type of
for further finishing by the well known technique of elec metallic device capable of being electropolished and requir
tropolishing. Stents being relatively small and fragile are ing an ultrasmooth Surface.
well Suited to electropolishing, but not to grinding, vibra In order to accomplish the electropolishing process, the
tion, or tumbling to attain a Smooth finish. cathode 10 and anode 20 are submerged in an electrolytic
Sometimes referred to as “reverse plating, the process of solution. In FIG. 1, the cathode or tubular member 11 is
electropolishing actually removes metal from the Surface shown Submerged in an electrolytic Solution 24 which is
desired to be smoothed. Electropolishing is an electrochemi held in a container 25 that is commonly known. The anode
cal process to Smooth metal Surfaces by dissolution of metal, 20 or metallic device 21 has not yet been submerged in the
which takes place more rapidly at high points on the metal 25 electrolytic solution and positioned within the tubular mem
Surface. The metal stent is rendered anodic (+) and is ber. As shown in FIG. 2, the electropolishing process is
immersed in a liquid electrolytic Solution along with a metal commenced when the anode or metallic device is positioned
cathode (-). Current is applied and flows from the anode, within the tubular member, in this case wire mesh tube 17,
polarizing it, thus encouraging the metal ions of the stent to by positioning the metallic device substantially within the
diffuse through the solution to the cathode. 30 wire mesh tube.
A special feature of electropolishing is the creation of The stent is composed of an alloy that includes cobalt and
current differentials across the microscopic surface of the chromium in an amount totaling at least fifty percent by
anode. The current density is greatest at high points on the weight of the alloy. This cobalt-chromium alloy is formed
surface and lowest at the low points. The rate of the into a tube and laser cut to form a stent configured in a lattice
electrochemical reaction is directly proportional to the cur 35 arrangement consisting of metal struts with gaps therebe
rent density so that increased current density at the raised tween as is known in the art. After the stent is formed by
points causes the anodic metal to dissolve faster at these laser cutting, it may optionally be descaled by dipping the
points thus leveling the surface material. The smoothed stent into a bath of about 9 parts of 37% concentrated
Surface of many metals can, with Sufficient electropolishing hydrochloric acid (HCl) to 1 part of 30% concentrated
techniques including use of the proper electrolytic solution, 40 hydrogen peroxide (HO) for approximately five minutes.
be made Sufficiently Smooth to an extent as to become shiny The descaling procedure is thereafter completed by ultra
and reflective. The finish may also be dependent on the level Sonically rinsing the stent, preferably in distilled water, at
of current applied, the duration of applied current, and the about 58° Celsius for about two minutes and then air dried.
temperature of the electrolytic solution. If after examination under a microscope residual slag
Referring to FIG. 1, a cathode 10 is provided in the form 45 remains, the descaling process acid bathing, ultrasonic rins
of a tubular member 11. The tubular member has a first end ing, and drying should be repeated. A successful stent
12 and a second end 13, with an opening 14 extending descaling should yield slag-free stents in preparation for
therethrough from the first end to the second end. In one Subsequent electropolishing.
embodiment as depicted in FIGS. 1 and 2, a wire 15 is Alternatively, the descaling procedure may be skipped
attached to a wire mesh tube 17 in which a lattice-type mesh 50 and the laser-cut stent may be electropolished with the
extends substantially from the first end to the second end of Solution of the present invention as a first step.
the tubular member. In another embodiment, the tubular In preparation for the electropolishing of the stent, the
member 11 is in the form of a wire coil 16 that is generally electrolytic solution of the present invention is prepared.
in the shape of a helix or a spiral While the tubular member While under a vented hood, and at standard conditions, 5 ml
11 of FIGS. 1 and 2 is in the form of a continuous wire mesh 55 of 37% concentrated hydrochloric acid (HCl) is poured into
tube 17, the tube can be non-continuous (e.g., two or more a beaker. Then, 5 ml of 85% concentrated phosphoric acid
arcuate sections with a longitudinal space between sections) (HPO) is poured into the HC1. Next, 30 ml of 98%
and still operate as the cathode. Further, tube 17 can have concentrated sulfuric acid (HSO) is poured into the beaker.
other configurations such as an hour glass shape or a tapered Phosphoric acid is not reactive with hydrochloric acid and
shape to Suit a particular application. 60 thus should be added to the HCl before the sulfuric acid is
As shown in FIG. 1, an anode 20 is formed by a metallic added in order to prevent a violent reaction between the HC1
device 21. For purposes of discussion, and by illustration and sulfuric acid. Once the phosphoric acid has been added
only, a metallic stent 22 is depicted as forming the metallic to the HCl, the sulfuric acid can be slowly poured into the
device. A current conducting member 23 (Such as a wire) is solution without a violent reaction. For this reason, the 6:1:1
attached to one end of the metallic device in order to 65 Solution of the present invention is less reactive during
complete the electrical circuit between the anode and cath preparation and easier to handle than the prior art 3:1
ode. Importantly, and as shown in FIG. 2, the cathode or solution which only has HCl and sulfuric acid as compo
 US 7,357,854 B1
10
nents. All three acids, whether individually or as a mixture, 18 mm-long stent, generally four to seven cycles, and
are extremely corrosive. Contact with skin or tissue, whether typically five, are employed to produce an ultrasmooth and
through liquid spill or in the form of exposure to fumes, can shiny Surface using the 6:1:1 solution of the present inven
be severely injurious. Appropriate safety gear should be tion. Longer stents have more Surface area than shorter
employed when handling and disposing of Such acids. 5 stents and may require more time in the acid solution and
As it is known that HCl has a tendency to boil off, optimal results for any particular size and length of stent can
possibly leaving a Zero or negligible HCl content in a liquid easily be determined. The length of time the product or stent
mixture, this invention also contemplates a solution com is in the Solution is proportional to the Surface area being
prising about 6 parts of about 98% concentrated sulfuric acid electropolished. The greater the surface area, the more time
(HSO) and about 1 part of about 85% concentrated phos 10 the product or stent is exposed to the solution. The stent is
phoric acid (HPO). thereafter cleaned ultrasonically in a distilled water bath at
In other embodiments, the electrolytic solution contains a temperature of 58° Celsius and subsequently air dried.
ethylene glycol and/or ethylene glycol derivatives as a first The ratio of the height of the cathode to stent length can
component and an acid as a second component. In these range from about 1:1 to about 8:1. At a 1:1 ratio, the stent
embodiments, equal parts by Volume of ethylene glycol, 15 ends are likely to be polished less than at a ratio of 8:1. The
ethylene glycol bisthioglycolate and ethylene glycol diac ratio of the tubular member diameter to the stent diameter
etate are combined to form the first component. In one can range from about 5:1 to about 10:1. Cycle times also can
embodiment, the electrolytic solution is then prepared by vary and range from 6 to 8 seconds for cobalt-chromium
pouring 30 ml of 98% concentrated sulfuric acid (the second stents that are about 18 mm in length when a current of about
component) into the beaker and then adding about 10 ml of four amperes is used. Alternatively, a lower current may be
the ethylene glycol mixture (the first component). In another used over a longer cycle time. In one embodiment, a cycle
embodiment, the electrolytic solution is prepared by pouring lasts about 40 to 45 seconds with a current of one to two
5 ml of 37% concentrated hydrochloric acid into the beaker, amperes.
adding 5 ml of the ethylene glycol mixture, and then adding The present invention electropolishing apparatus also
25 ml of 98% concentrated sulfuric acid. In yet another 25 optionally includes means for circulating the electropolish
embodiment, the electrolytic solution is prepared by pouring ing solution through the stent 22 and the tubular member 11.
25 ml of 98% concentrated sulfuric acid into the beaker, Various devices can be used to circulate the electrolytic
adding 5 ml of 85% concentrated phosphoric acid and then Solution and can include, for example, a circulation pump
adding 5 ml of the ethylene glycol mixture. for rotating or oscillating, a stir bar, or a re-circulation pump.
Forming the anode 20, the stent 22 in one embodiment is 30 It is preferred that the solution be gently moved as opposed
18 mm long and is mounted on a stainless Steel, titanium or to a vigorous movement so that it does not interfere with the
other metallic mandrel, which is conductively attached to a electropolishing process.
stainless steel clip. As is known in the art, there are a wide The stent may optionally be further processed with addi
range of stent lengths available and reference to an 18 mm tional electropolishing cycles, typically two to four, using a
long stent is for illustration only. The clip is conductively 35 proprietary solution sold under the name E272 manufactured
attached to a titanium rod to which the wire 23 is attached by ESMA, Inc., South Holland, Ill. It is believed that this
at the opposing end of the rod to the positive terminal of a Solution is a mildly acidic Solution containing glycol ethers
controllable power Supply capable of Supplying one to seven and glycol esters. This final step may not be needed, as the
amperes at up to twenty four volts DC. The amperage and stent Surface is ultrasmooth and shiny following the elec
Voltage can vary and in one embodiment the power Supply 40 tropolishing treatment using the solution of the present
provides one to seven amperes at up to twenty one volts. invention. However, depending on the degree of smoothness
Wire 15 is attached to the negative terminal of the power and shine required, additional processing with the final E272
Supply and is terminated at the cathode 10, Such cathode electropolishing solution may be desired, particularly if the
formed from 90% Platinum and 10% Iridium clad over a initial descaling treatment was not performed. Use of both
Niobium core. For use with an 18 mm long stent, for 45 the initial descaling treatment and final E272 electropolish
example, the cathode or tubular member 11 is about 20 to 50 ing step, however, are generally not necessary to produce a
mm long and 4 to 70 mm in diameter and is Submerged into highly ultraSmooth and shiny stent Surface. Typically, one
the acid mixture so that the tubular member is suspended processing step is eliminated in the treatment of a stent using
substantially in the acid. In one embodiment, the tubular the solution of the present invention, either the initial
member is about 36 to 40 mm high (or long) about 14 to 20 50 descaling treatment or the E272 final electropolishing step.
mm in diameter. The anodic stent 22 is then lowered and The electropolishing procedure employing the solution of
vertically submerged into the electrolytic acid solution 24 the present invention removes material from the stent Sur
and positioned through the tubular member so that the ends face greatly smoothening the Surface. Electropolishing also
of the stent are substantially equidistant from the tubular provides a protective corrosion-resistant oxide layer on the
member. The clip remains out of the solution. The power 55 stent Surface.
Supply is thereafter energized and adjusted altering the Compared to the prior art 3:1 solution, the processing time
current controller to supply four amperes of current to the using the 6:1:1 solution of the present invention is reduced
solution for a period of approximately eight seconds. While by about half. To acceptably polish a stent having a tubular
the disclosed embodiment shows stent 22 submerged in a wall with a wall thickness of about 0.005 inch using the prior
vertical orientation, it can be rotated into other orientations 60 art 3:1 solution, about 12 to 14 electropolishing cycles were
such as, for example, from 0° to 90° relative to vertical. typically required, in addition to a descaling treatment
The stent 22 is then removed from the electrolytic solu consisting of a 5 minute acid bath followed by 2 minutes of
tion 24, rinsed with water, and turned axially on the mandrel ultrasonic cleaning. This required about 8-12 minutes of
to expose the stent Surface beneath the mandrel contacts to processing time per stent. However, the present Solution can
the acid. The remounted stent is then resubmerged in the 65 polish a stent in about 5 electropolishing cycles without any
solution for additional cycles of electropolishing with descaling treatment, for a total processing time of about 2-3
another rinse and another turn relative to the mandrel. For an minutes.
 US 7,357,854 B1
11 12
The ethylene glycol solution of the present invention also produces an ultrasmooth surface finish while the prior art
reduces the processing time for electropolishing cobalt solution is unable to achieve such a finish on 0.004 inch
chromium stents. The ethylene glycol Solution produces a thick stents within the target dimensions. As a result, the
smooth and shiny surface finish without using the E272 final prior art solution can be unacceptable for use on 0.004 inch
electropolishing solution. Thus, the final E272 electropol thick stents, while the 6:1:1 solution of the present invention
ishing step may be eliminated, reducing process time and the proves successful.
number of different solutions needed. However, experiments Experiments were also performed to determine the water
testing the solutions of the present invention indicated that contamination thresholds of the solutions. Water contami
Solutions containing a mixture of equal parts by Volume of nation was defined as the amount of water that enters the
ethylene glycol, ethylene glycol bisthioglycolate and ethyl 10 Solution (by carryover, absorption, etc.) before polishing
ene glycol diacetate as a component were able to Success ceases and the Solution needs to be exchanged. The experi
fully polish stents only when used within about one day after ments on water contamination revealed that the 3:1 prior art
being prepared. After about a day, these solutions had Solution ceased to further polish stents at approximately a
difficulty carrying the 4 ampere current and were ineffective 2.5% water content level while the 6:1:1 solution still
in polishing the stents. The 6:1:1 solution, on the other hand, 15 performed suitably with over a 10% water content level. The
is stable and has an indefinitely long shelf life. The 6:1:1 6:1:1 Solution, therefore, has a higher resistance to water
Solution may be prepared and used at any later time to contamination than the 3:1 prior art solution, requiring less
Successfully polish a stent. frequent replacement.
FIG. 3A illustrates, in the form of a photograph, the In addition, the longevity of the 6:1:1 solution of the
Surface finish of an 18 mm-long cobalt-chromium stent of present invention and the prior art 3:1 solution were also
the present invention having a tubular wall with a wall studied. Longevity was defined as the total number of stents
thickness, before treatment, of about 0.004 inch and elec that could be acceptably polished per unit volume of solu
tropolished with the 6:1:1 solution of the present invention tion. The ability of a solution to polish is reduced as the
to a strut thickness at the center ring of 0.0031 inch. No metal ion and water concentrations increase. Using stents
descaling treatment or final E272 electropolishing step was 25 with wall thicknesses before treatment of about 0.004 inch,
employed. FIG. 3A reveals a surface finish that is ultras 60 ml of the prior art 3:1 solution polished 12 stents before
mooth and shiny without Surface defects such as pock marks the solution failed, while 60 ml of the 6:1:1 solution of the
or surface pits. FIG. 3B illustrates the sidewall finish of the present invention polished 17 stents before the solution
stent in FIG. 3A. FIG. 3B reveals ultrasmooth and shiny failed. Therefore, the 6:1:1 solution of the present invention
sidewalls. 30 has increased longevity compared to the prior art 3:1 solu
FIG. 4A illustrates, in the form of a photograph, the tion, requiring less frequent replacement.
surface finish of an 18 mm-long cobalt-chromium stent Concentration of the acid components of the present
composed from a tube having a tubular wall with a wall invention may be found in convenient reagent grades of
thickness, before treatment, of about 0.004 inch electropol about 37% concentrated hydrochloric acid, about 98% con
ished using the prior art 3:1 electrolytic solution to a strut 35 centrated sulfuric acid and about 85% concentrated phos
thickness at the center ring of 0.0031 inch. No descaling phoric acid. Typically, reagent grade acids vary to some
treatment or final E272 electropolishing step was employed. extent in concentration from the concentration depicted on
FIG. 4A reveals surface pitting, pock marks and Surface the container label, usually within 3% of their stated con
scratches that remained after electropolishing under similar centration. Decreasing Smoothness of the stent Surface is
test conditions and to the same center strut thickness as with 40 experienced by varying the six to one to one ratio of the
the solution of the present invention. FIG. 4B illustrates the acids substantially in either direction.
sidewall finish of the stent in FIG. 4A. FIG. 4B reveals As is the nature of many parameters of various processes,
sidewalls with some rough edges and Scratches. Thus, it can parameters of the electropolishing process may be altered by
be seen that use of the 6:1:1 electrolytic solution of the degree to provide similar results. It is the intention to include
present invention on cobalt-chromium parts cut from 0.004 45 Such modification, within the scope of the invention, and as
inch thick tubes produces a surface finish that is Substan is known in the art, of time, temperature, humidity, pressure,
tially smoother than that achieved by the prior art solution Voltage, Current, cathode material, cathode dimension,
for the same thickness. The 6:1:1 solution of the present degree of descaling, rinsing, as well as other variable
invention also produces an ultrasmooth and shiny finish on parameters not heretofore mentioned.
a stent composed from a tube having a wall thickness of 50 The present invention satisfies a great need for an elec
about 0.005 inch. trolytic solution to electropolish a product or device made
Using a Wyko NT3300 Syrface Profiler (from Veeco from cobalt-chromium, Such as a cobalt-chromium stent, to
Instruments, Inc., Woodbury, N.Y.), roughness average (Ra) consistently produce an ultrasmooth Surface finish, and
values were measured on cobalt-chromium stents elec satisfies a great need for a cobalt-chromium stent possessing
tropolished with the solutions of the present invention and 55 Such a surface. Additionally, the present invention satisfies
with the prior art 3:1 solution. A final electropolishing step the need for a method to electropolish a cobalt-chromium
using the E272 solution was performed on the stents in these stent to Such a Surface finish.
measurements. Roughness average values for stents elec The embodiments heretofore discussed are in no way
tropolished to a target strut thickness at the center ring of intended to limit the scope of the invention. Various changes
0.0032 inch using the 6:1:1 solution of the present invention 60 and improvements may also be made to the invention
were measured to be ultrasmooth at approximately 101 nm. without departing from the scope thereof.
However, to attain comparable roughness average values, What is claimed:
stents electropolished with the prior art 3:1 solution had to 1. A method of treating a cobalt-chromium device that
be overpolished to a final strut thickness at the center ring of includes electropolishing the device in an electrolytic solu
0.0024 to 0.0026 inch, far outside the target thickness. Thus, 65 tion, comprising:
experimental trials confirm that use of the electrolytic solu combining about 1 part by Volume of a first component
tion of the present invention on cobalt-chromium parts Selected from the group consisting of ethylene glycol,
 US 7,357,854 B1
13 14
ethylene glycol derivatives and mixtures thereof and at combining about 1 part by Volume of a first component
least about 2 parts by Volume of a second component Selected from the group consisting of ethylene glycol,
that is an acid in solution selected from the group ethylene glycol derivatives and mixtures thereof and at
consisting of Sulfuric acid, hydrochloric acid, phospho least about 2 parts by Volume of a second component
ric acid and mixtures thereof, wherein the first compo that is an acid in solution, wherein the first component
nent is a mixture of ethylene glycol, ethylene glycol is a mixture of ethylene glycol, ethylene glycol
bisthioglycolate and ethylene glycol diacetate; and bisthioglycolate and ethylene glycol diacetate; and
Submerging the device in the solution. Submerging the device in the Solution.
2. The method of claim 1, wherein the solution comprises 10. The method of claim 9, wherein the solution com
about 1 part by volume of the first component and about 3 10 prises about 1 part by volume of the first component and
parts by Volume of the second component, the first compo about 3 parts by volume of the second component, the first
nent being a mixture of about equal parts by Volume of component being a mixture of about equal parts by Volume
ethylene glycol, ethylene glycol bisthioglycolate and ethyl of ethylene glycol, ethylene glycol bisthioglycolate and
ene glycol diacetate and the second component being about ethylene glycol diacetate and the second component being
98% by weight concentrated sulfuric acid. 15 about 98% by weight concentrated sulfuric acid.
3. The method of claim 1, wherein the solution comprises 11. The method of claim 9, wherein the solution com
about 1 part by volume of the first component and about 6 prises about 1 part by volume of the first component and
parts by Volume of the second component, the first compo about 6 parts by volume of the second component, the first
nent being a mixture of about equal parts by Volume of component being a mixture of about equal parts by Volume
ethylene glycol, ethylene glycol bisthioglycolate and ethyl of ethylene glycol, ethylene glycol bisthioglycolate and
ene glycol diacetate and the second component being a ethylene glycol diacetate and the second component being a
mixture of about 5 parts by volume of 98% by weight mixture of about 5 parts by volume of 98% by weight
concentrated sulfuric acid and about 1 part by volume of concentrated sulfuric acid and about 1 part by volume of
37% by weight hydrochloric acid. 37% hydrochloric acid.
4. The method of claim 1, wherein the solution comprises 25 12. The method of claim 9, wherein the solution com
about 1 part by volume of the first component and about 6 prises about 1 part by volume of the first component and
parts by Volume of the second component, the first compo about 6 parts by volume of the second component, the first
nent being a mixture of about equal parts by Volume of component being a mixture of about equal parts by Volume
ethylene glycol, ethylene glycol bisthioglycolate and ethyl of ethylene glycol, ethylene glycol bisthioglycolate and
ene glycol diacetate and the second component being a 30 ethylene glycol diacetate and the second component being a
mixture of about 5 parts by volume of 98% by weight mixture of about 5 parts by volume of 98% by weight
concentrated sulfuric acid and about 1 part by volume of concentrated sulfuric acid and about 1 part by volume of
85% by weight phosphoric acid. 85% by weight phosphoric acid.
5. The method of claim 1, wherein the device is sub 13. The method of claim 9, wherein the device is sub
merged in the solution for a period of time that is propor 35 merged in the Solution for a period of time that is propor
tional to the surface area of the device. tional to the surface area of the device.
6. The method of claim 1, wherein the electropolished 14. The method of claim 9, wherein the device is sub
device is a medical device. merged in the Solution for a period of time that is propor
7. The method of claim 6, wherein the medical device is tional to the surface area of the device.
a Stent. 40 15. The method of claim 9, wherein the medical device is
8. The method of claim 7, wherein the stent is submerged a Stent.
in the solution for a period of time that is proportional to the 16. The method of claim 8, wherein the stent is submerged
Surface area of the stent. in the solution for a period of time that is proportional to the
9. A method of treating a cobalt-chromium medical device Surface area of the stent.
that includes electropolishing the device in an electrolytic 45
Solution, comprising: