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Prakash Sojitra1*, Chhaya Engineer1, Ankur Raval1, Devesh Kothwala1, Arpit Jariwala1, Haresh
Kotadia1, Subodh Adeshara1 and Girish Mehta2
1
Research & Development Division, Sahajanand Medical Technologies, Surat -395003
2
S.V. National Institute of Technology, Surat-395007
*Corresponding author. prakash.med@sahmed.com
Received 10 December 2008, Accepted 30 May 2009, Published online 8 November 2009
Smooth surface is prerequisite for all implantable medical devices to increase biocompatibility.
Electropolishing is an effective process for improving surface smoothness of the cardiovascular devices. In
this study, electropolishing was employed on laser cut L605 Co-Cr alloy cardiovascular stents to increase
surface smoothness. Acid descaling was used as a pretreatment before electropolishing for effective removal
of metal oxides generated due to laser-cutting process. Effect of temperature during electropolishing on the
rate of material removal was also evaluated. Passivation was carried out after electropolishing of stent to
enhance its corrosion resistance in biological environment. The stent was characterized by Optical
Microscopy for strut dimension analysis, Scanning Electron Microscopy and Atomic Force Microscopy for
its surface smoothness, gravimetric analysis for evaluation of material removal uniformity, EDAX analysis for
elemental composition and balloon expandability. It was found that elemental composition of stent remains
unaltered after series of chemical treatments including the acid descaling and the electropolishing. Surface
roughness of stent after electropolishing was reduced to significant level and such electropolished stents
also demonstrated uniform expansion under specific required conditions. © Society for Biomaterials and
Artificial Organs (India), 20081210-31.
and excess drag during travel to the stenotic Minitubes, France and used as received. The
site as well as damaging the endothelium lining material composition in wt % as per supplier
of the vessel wall [3]. Surface roughness also specification was Cr (19.91), Ni (10.39), W
influences the amount of protein adherence as (14.96), Fe (1.80), Si (0.17), Mn (1.21), C
it determines the contact area [4]. Immediately (00073), P (0.010), S (0.002) and Co (balance).
following and in concert with the adsorbed These tubes were utilized for laser cutting (Star
proteins after stent implantation, the stent Cut Tube 18, Rofin Laser, Germany) to obtain
surface properties will determine platelet and stents of 16 mm length. Prior to laser cutting,
leucocyte adherence. As such, the surface tubes were initially cleaned using deionized
properties determine thrombogenicity, water in an ultrasonic agitation bath for 15 min
inflammation and vascular wound healing. As and were dried by hot air dryer (Philips Flex
the surface characteristics influence directly the 1000, Japan). PTCA (Percutaneous
biocompatibility of the stents, a smooth surface Transluminal Coronary Angioplasty) balloon
obtained after electrochemical polishing can catheter used during the study was procured
minimize thrombosis effectively and also has a from Natec, Mauritius. It was made up of Nylon-
potential beneficial effect on neointimal 12 material with PTFE coated stainless steel
hyperplasia [5]. Surface prepared by hypotube shaft. Two radiopaque markers were
electropolishing [6-9] have shown improved the located underneath the balloon, which
performance of stents. fluoroscopically marked its working length.
Dimensions of balloon used was 3.0 x 17 mm,
The aim of this research was to prepare smooth where 3.0 mm denotes the maximum diameter
surface of L-605 coronary stent by achieved at nominal inflation pressure and 17
electropolishing and characterize the surface mm denotes usable balloon length between
properties of stent after series of fabrication two radio opaque markers. All Ranbaxy make
processes. Acid descaling with the application chemicals sulfuric acid, hydrofluoric acid,
of ultrasonic waves has been effectively utilized perchloric acid, nitric acid, iso propyl alcohol
to remove laser generate metal oxides and and glycerol were of AR grade.
burrs. To improve surface smoothness of the
stent, a novel electrolyte and EP process has Acid Descaling
been investigated for coronary stents. Effect of
various process parameters for electropolishing Laser micromachining generates slag,
process has been optimized to get smooth and unwanted metal oxides and burrs at stent
uniform surface. In order to characterize the structure edges and inner surface. To achieve
surface morphology; various sophisticated high degree of smooth surface after
analytical techniques such as scanning electron electropolishing, unwanted scale must be
microscopy (SEM), and atomic force microscopy removed from the stent. Acid descaling was
(AFM) were explored. Energy dispersive X-ray performed on laser cut stent to remove these
analysis (EDEX) was used to determine the slag, metal oxides and burrs. As-received laser-
subsurface composition of metal after different cut stents were first cleaned ultrasonically with
stages of processes. Passivation process has deionized water and dried by hot air drier. Acid
also been carried out as an approach to improve descaling was performed on the laser-cut
the corrosion resistance properties of metal stents by immersing them in to descaling
when it is used as an implantable biomaterial. solution having HF, HNO3 and deionized water,
Expansion properties of investigated stent have at 45 °C for 200 minutes using ultrasonic waves
been verified after crimping and expanding the operating at 43 kHz. Thermostat of ultrasonic
stent on balloon catheter and results were cleaner (Branson 3510-DTH, USA) was used
collected as SEM micrographs. to maintain constant temperature of water bath
After acid descaling treatment, the descaled
Materials and methods stents were cleaned ultrasonically using
deionized water for at least 15 minutes to
The L-605 Co-Cr alloy (ASTM F 90-07) remove traces of descaling agents and were
annealed tubes (outer diameter 1.60 mm, then dried by hot air drier. Composition of the
thickness 110-115 µm) were procured from acid descaling solution and electrolyte
Characterization of L-605 Cobalt Alloy Cardiovascular Stent 57
formulation are 3ml HF, 20ml HNO3 and rest 4OH- - 4Electrons = 2H2O + O2
deionised water to make it 100ml.
Cathodic: 2H+ + 2 Electrons = H2
Electropolishing
Total Reaction: Metal Ions + Electrons = Metal
In order to achieve smooth surface, improved
fatigue resistance, low friction, improved wetting Important parameters which affect the electro-
and bonding properties of a very clean surface, polishing process are current density, compo-
material must under go surface treatment sition of electrolyte, temperature, process time,
process which can produce defect free surface, hydrodynamics of electrolyte and the area of
remove irregularities, appropriate leveling and substrate to be electropolished [13].
smoothness. Electro-chemical polishing is the
process of obtaining better smoothness on the Schematic of electropolishing set-up and stent
surface of the stent by anodically polarizing it in arrangement is shown in figure 1. A glass co-
highly conductive electrolytes. It is classified into ntainer was used as the electrolytic polishing
two processes: anodic leveling and anodic cell (100 mm diameter and 500 mm high). A DC
brightening [10]. A negatively charged ionic layer, rectifier (Testronix 92D) was used for power
usually referred to as “Anodic Layer” is formed supply (30V and 10A maximum). The descaled
at the surface of the work-piece mounted on the stent was connected to anode and a 304
anode, which is positively charged and chromic stainless steel circular ring (diameter: 90 mm,
ions are concentrated in this layer. The thickness: 1 mm) was used as the cathode.
electrochemical reactions are as follows [11, The distance between these two electrodes was
12]. fixed at 45 mm. Electropolishing process was
performed with continuous stirring of electrolyte
Anodic: Metal - Electron(s) = Metal Ion by magnatic paddle. Optimized electropolishing
parameters are Stent size 16mm; Volume 9V;
58 P. Sojitra, C. Engineer, A. Raval, D. Kothwala, A. Jariwala, H. Kotadia, S. Adeshara, G. Mehta
Current 0.24A; Temperature of 55ºC and Time environment [14]. Passivation was carried out
of 300s. The temperature of the electrolyte was on electropolished stent using aqueous solution
maintained by heating coil. After electropolishing of 25% (v/v) nitric acid in deionized water for 30
process the stent was removed from the bath, minutes. Stents were immersed in the
rinsed with deionized water spray several times passivation solution which was kept in a beaker
and dried with hot air drier. maintained at 75°C using constant temperature
water bath. To prevent photolytic degradation
Effect of Electropolishing Temperature on of nitric acid, glasswares used for passivation
Material Removal process were of amber color. After 30 minutes,
the stents were taken out and washed
Electropolishing temperature remarkably thoroughly with deionized water several times
influences the material removal rate. To analyze then with 25% sodium carbonate solution to
the effect of temperature on electropolishing neutralize acid traces. Again stents were rinsed
process of stents, descaled stents were with deionized water for complete removal of
electropolished at different electrolyte sodium carbonate. Finally the stents were
temperature (45º, 50º, 55º, 60º and 65ºC) and stored till further investigation separately in a
reduction in stent weight was compared for closed glass container filled with isopropyl
each process temperature by gravimetric alcohol to avoid microbial contamination.
analysis. All other parameters (current, voltage,
time, stent size) were kept constant during the Scanning Electron Microscopy and EDAX
analysis. analysis
Gravimetric Analysis of Stents
Evaluation of the qualitative surface morphology
Gravimetric analyses of each stent after laser- and elemental analysis was performed using
cutting, acid descaling and electropolishing Scanning Electron Microscopy (Philips XL30
was performed by an electronic analytical ESEM TMP). It is preferable that the processes
balance (Citizen CX-265, Germany, and involved in the manufacturing of stent should
Accuracy: 0.01 mg). Dimension measurement not alter the chemical composition and thus
of each stent was carried out using a light optical mechanical performance of the alloy used to
microscope (OLYMPUS SZX 12) attached with prepare the stent. The elemental analysis by
CCD camera, which was calibrated with 1/100 EDAX was carried out simultaneously to
mm calibration strip (Model OB-MM, Olympus, evaluate material composition after different
Japan) before the analysis. Percentage weight stages of stent fabrication and chemical surface
loss and width reduction of each stent was improvisation processes.
estimated by the following formula.
Atomic Force Microscopy
%Weight loss = (weight before EP – weight after
The surface topology and quantitative
EP)/ weight before EPx100
roughness measurements were performed on
%Width Reduction = (width before EP – width acid descaled and electropolished stent by
after EP)/width before EPx100 Atomic Force Microscopy (AFM). Roughness
was measured by means of AFM instrument di-
For a batch, 10 stents were analyzed as above CP II, Veeco Asia. The samples were placed on
and average of the data was considered. platform of evaluation device and analysis area
was monitored by attached CCD camera
Passivation during the analysis. Entire analysis setup was
kept on antivibration device for the accurate
Passivation process was employed after measurement of roughness. The evaluation
electropolishing to enhance corrosion area for AFM analysis was 30x30 micron.
resistance of the stent. The purpose was to
enhance spontaneous formation of the Balloon Expandability of Stents
protective passive film in order to achieve Cr2O3
enriched layer on the stent surface to improve To examine expandability of the stents after
corrosion resistance of stent under biological surface treatment, they were expanded using
Characterization of L-605 Cobalt Alloy Cardiovascular Stent 59
commercial PTCA balloon catheter. Passivated Table 4: Material removal rate at different
stents (16mm long) were crimped on the temperature
3.0x17mm balloon by means of automatic
crimping machine SC 500 (Machine Solutions
Inc, USA). The crimped stents were expanded
by inflation device (Medtronic, Skimed- Sedat,
USA). The pressure gauge was attached with
the expansion device to measure the pressure
applied to the balloon. Sterile water was used
to inflate balloon for expansion of stents at
nominal pressure of 6 bar as prescribed in
compliance chart provided by balloon
manufacturer. The balloon was kept dilated for
approximately 45–60 sec and then deflated. The
Gravimetric Analysis
crimped and dilated stent symmetries were
inspected by scanning electron microscopy. Table 5 represents the average data of
gravimetric analysis of 10 stents and Table 6
Results and Discussion
represent those of strut widths / width reduction
Effect of Electropolishing Temperature on and wall thickness reduction of the laser cut,
Material Removal descaled and electropolished stent.
As shown in table 4 it can be seen that material As shown, the laser cut stent has an average
removal rate increased with increase in process weight of 23 mg and a strut width of 101.5 µm.
temperature. The rate of material removal was After acid descaling, there was a weight loss of
controlled between 50-60º C. Fig. 2(a) and 2(b) 6.95 % and the stent strut width was decreased
indicates optical images of the stent by 6.40 %. The reduction in stent weight and
electropolished at 40 and 65ºC temperature dimension is due to the removal of metal oxides
respectively. Electropolishing at lower and excess slag formed during laser cutting of
temperature resulted rough surface where as stent. Due to electrochemical polishing, the
EP at high temperature resulted uncontrolled weight and strut width of the stent decreased
material removal with the uneven surface by 28.59 % and 40.88 % respectively. Therefore,
smoothness. Therefore temperature was after electropolishing the final average
optimized at 55ºC for the electropolishing dimension of the stent strut was decreased to
process. Surface quality as well as dimensional 60 µm from 105 µm. Figures 3, 4 and 5 illustrate
data also supports this temperature range of uniform reduction in weight, strut width and wall
electropolishing process as revealed by SEM thickness after each process. The data revealed
analysis. that the rate of removal of material after
electropolishing is excellently controlled.
EDAX Analysis
0.007
120
0.006
0.004 80 Lasercut
0.003 60 Descaled
0.002 40 Electropolished
0.001 20
0 0
40 45 50 55 60 65 1 2 3 4 5 6 7 8 9 10
Temperature No of Stents
Figure 3: Temperature effect Vs gravimetric Figure 5: Plot of stent width after Laser
analysis cutting, Descaling and Electropolishing
20 120
Weight (mg)
100
15 Laser Cut
80
Descaled Descaled
10 60
Electropolished EP
40
5
20
0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
No of Stents No. of stents
Figure 4: Plot of stent weight after Laser Figure 6: Plot of stent wall thickness after
cutting, Descaling and Electropolishing Descaling and Electropolishing
Figure 7: Laser cut stent (a) Inner Surface (b) Cutting Zone
Atomic Force Microscopy Figure 12. The stent was found crimped on
balloon catheter without overlapping of struts.
Figure 11 (a) and 11 (b) shows AFM images of The crimping profile of stent for 3.0 mm
acid descaled stent and electropolished stent diameter balloon was 0.93 mm measured
surface respectively in 30x30 micron evaluation using contact micrometer. Low crimping profile
area. Comparison of both the images depicts ensures that stent can easily navigate through
that electropolished stent has significantly small vessels and tortuous blockages. The SEM
reduced surface roughness compare to acid investigation of expanded stent (Figure 13)
descaled stent. This also reveals efficacy of revealed that at 6 bar of applied pressure, the
electropolishing process to improve surface stent was uniformly expanded to a diameter of
smoothness. It represents 78.66 % reduction approximately 3.0 mm. None of the struts were
of surface roughness after electropolishing disproportionately expanded and appropriate
process. straightening of struts observed between
alternate links. Electropolishing process has
Balloon expandability of electropolished stent significant influence on stent expansion
The scanning electron microscopy images of properties which is important in stent
implantation during angioplasty because
stent crimping on balloon catheter is shown in
uneven material removal can lead to improper
scaffolding to artery.
Conclusion
Figure 10: EDAX Analysis, (a) Laser cut stent, (b) Acid descaled stent (c) Electropolished stent
Characterization of L-605 Cobalt Alloy Cardiovascular Stent 63
Figure 11: AFM images of stent in 30 X 30 Micron area (a) Acid descaled (b) Electropolished
stent
Figure 12: SEM of Balloon crimped stent Figure 13: SEM of expanded stent
surface smoothness as confirmed by the SEM Companies for providing financial assistance
and AFM analysis. EDAX analysis reveals no to carry out the research work. Also wishes to
significant change in elemental composition of thanks Dr. Subodh Adeshara & Mr. Sanjay Shah
stent after acid descaling or electropolishing for enthusiastic encouragement. Contributions
process. AFM analysis shows significant from research team of Sahajanand Medical
reduction in surface roughness (78.66%) of Technologies (Kamal Revdiwala, Ami Raval,
stent after electropolishing process. Himanshu Patel, Jaynish Tailor, Laxman Upale,
Nilesh Kadu and Rahul Patel) are also gratefully
Acknowledgement acknowledged.
We express our sincere gratitude to Mr. Dhirajlal
Kotadia, Chairman, Sahajanand Group of
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