Laser Material Processing

Why the annealing of 316LVM-Stents is so important

Dr. C. Meyer-Kobbe B.H. Hinrichs

Sarstedt, December 2002

MeKo Laserstrahl-Materialbearbeitung Kthe-Paulus-Strae 9-11 D-31157 Sarstedt / Germany www.meko.de

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The Importance of Annealing 316LVM Stents

C. Meyer-Kobbe and B.H. Hinrichs MeKo Laser Material Processing, Sarstedt, Germany Annealing has a considerable influence on the quality of stents and is possibly the most critical process in their manufacture because it determines the material properties of the stent. Improved methods for verifying the results of the annealing process are described. These give direct results of grain size and physical properties to thereby improve the quality of the final product. More precise verification delivers higher quality The results of laser cutting and electropolishing can be easily visually inspected by anyone who possesses a good microscope and has some experience in the final quality control of stents. Thus, laser cutting and electropolishing have been recognised as the main quality factors in the manufacture of stents. However, annealing is another key quality factor in the process chain of stent manufacture. The annealing process determines the final material properties of the stent such as grain size, ultimate tensile strength, break elongation, corrosion resistance, fatigue strength and surface quality. Therefore, it is obviously not sufficient to specify only the properties of the raw material. The outcome of the annealing process cannot be determined by visual inspection, but requires a more costly and demanding analysis of the material properties. In addition, a detailed understanding of material properties and annealing is necessary. The main aim of the following investigation was to improve the quality of annealing of 316LVM stents, mainly coronary stents. The final material properties of the stents were to be improved and a reliable method for verifying the results of the annealing process was to be identified. Material properties The quality of stents starts with the selection of the raw tube material. The two main factors here are the dimensional accuracy and the material properties of the tubing.

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The dimensional accuracy includes the outer diameter and wall thickness tolerances, the concentricity, the straightness of the tubing and the surface quality of inner and outer surfaces. Of these dimensional parameters, only the inner and outer surface quality can be improved at a later stage of the manufacturing process by electropolishing. The important material properties include material composition, purity or microcleanliness (content of nonmetallic inclusions), grain size and hardness or grade of strain hardening through cold work. These factors determine the physical properties of the material including tensile strength, break elongation, ultimate tensile strength, fatigue strength and other properties such as corrosion resistance. Most of these material properties are influenced and finally set by annealing. Stent tubes normally have a grain size of ASTM 7 to 8, which indicates grain sizes of 24-34 m. A typical cross section of a tube is shown in Figure 1. For the finished stent, it is desirable to obtain the finest possible grain size. Generally, the wall thickness of the tube should show a minimum of 8 to 10 grains. A finer grain size reduces the risk of a stent strut breaking. The precipitation along the grain boundary is also minimised and the fatigue resistance is improved.

Figure 1: Cross sections of a 3/4 hard stent tube

For tubes used for laser-cut stents, 3/4 is preferred because handling causes fewer problems. Harder tubes are stronger and, therefore, often straighter, and fully heat treated tubes can be bent easily. The outer surface of hard tubes is more scratch resistant whereas fully annealed tubes are sensitive to scratching because of the softer material.
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Figure 2 shows a typical stressstrain diagram of 3/4 hard tubing. The diagram illustrates an ultimate tensile strength of more than 900 N/mm2 and a break elongation of only 8-10 %. This low break elongation will almost certainly cause the stent struts to break during dilatation in the human vessel. Because the struts are not homogeneously expanded, strut regions with high distortion are critical and prone to break. Therefore, stents manufactured of 3/4 hard tubes have to be annealed. With the annealing, break elongations of usually more than 40% can be achieved, which contribute to preventing the strut from breaking and to achieving high fatigue resistance. Annealing also removes possible negative influences from the heataffected zone of the laser cut. In addition, the annealing process can be better optimised and controlled for tiny stents than for long tubes.

1000

800 stress in N/mm

600

400

200

0 0 2 4 strain in % 6 8 10

Figure 2: Stress/strain-diagram of hard stent-tubing

Based on this knowledge, the use of 3/4 hard tubing is advocated instead of annealed tubing as the raw material for stents. The annealing of hard stents must produce the following material properties: small grain size, high break elongation in combination, if possible, with excellent ultimate tensile strength. Indirectly, with these parameters high fatigue strength and corrosion resistance are achieved. To optimise all these properties an extensive investigation has been performed.

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Investigation of annealing Until now, the results of the annealing of stents have been indirectly controlled by the timetemperature curve of the furnace and, from time to time, by microhardness measurements in the cross sections of annealed stents. Both procedures are inappropriate. First, even if the timetemperature curve is correct, the result of the annealing can be unacceptable as a result of tube raw material with bad metallurgical properties (no absence of free ferrite phase, big gain size, low microcleanliness,). Second, conforming with EN ISO 6507-1: Metallic materials - Vickers hardness test Part 1: Test method, 1997 the microhardness is measured as the area of indentation of a small prism pressed into the material surface with a specific force. The standard states a minimum distance, from the middle of the indentation mark to the edge of the sample, of 2.5 times the diagonal of the indentation. For a tube with, for example, a wall thickness of 100 m, the maximum permitted diameter of indentation is 20 m, if the indentation is exactly in the middle of the cross section of the tube [1]. Economically speaking, this small indentation cannot be measured accurately. Therefore, this testing method is not suitable and should not be permitted for annealed stents. Finally, there is no reliable formula or diagram to convert the measured hardness into material strength or break elongation. For these reasons, the often applied microhardness measurement should be excluded from any stent inspection. The methods of choice The methods the authors apply for analysing stent material properties are microscopical grain examination and tension tests [2]. These methods give direct and exact results of the grain size and physical properties such as ultimate tensile strength and break elongation. To conduct the detailed analysis, stent tubes with dimensions of 1.8 x 0.14 mm were cut into hundreds of short pieces. These short tube samples are suitable for the tension tests; complete stents, because of their flexible structure, cannot be tested in the tension machine. The short tube pieces were annealed in two different furnaces: furnace 1 was a standard annealing furnace, and furnace 2 was specially designed for the heat treatment of stents. Furnace 1 can be considered to be the common method for annealing. It has been used to anneal tens of thousands of stents. In the investigation, this standard furnace
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was operated according to the validated and certified annealing procedure for stents. The results of this annealing process are given as a reference. The aim of the investigation was to improve the results of the annealing process achieved with the standard furnace 1, specifically with the help of the special furnace 2. For this, hundreds of annealing processes were completed with varying parameter settings to identify the most suitable settings to obtain the best annealing result. The main targets were to achieve a reliably high break elongation together with a homogenously fine grain size, which is not necessarily the same, and a high tensile strength. After the primary study, involving only one tube type (1.8 x 0.14 mm), other tube dimensions were investigated. To certify the annealing results, further experiments were conducted to verify the temperature homogeneity of the furnace, the reproducibility of the annealing curves, the influence of the annealing lot size, the influence of the position of single tube pieces inside the furnace and the reproducibility of the tension tests. These auxiliary experiments are not described in this article.

Results of the annealing All results of the investigations are average values and not extremes. Each result has been proved by several tests with the same annealing parameters. Figure 3 shows the typical grain structure and size achieved with the standard furnace 1. The original structure of the cold-drawn material has been totally eliminated. The grain size of ASTM 8-9 (20-24 m) is already smaller than the original raw tube material (compared with Figure 1). This grain size is acceptable provided the tubes wall thickness is not too thin after electropolishing. However, for a wall thickness or a strut size of less than 200 m, a finer grain size is recommended to avoid negative effects of too few grains across the wall thickness of the strut, especially a reduction in average break elongation. This negative effect has been confirmed by experiments with tubing of thinner wall thicknesses. For a tube-wall thickness of approximately 80 m, the average break elongation can be decreased by half.
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Figure 3: Typical structure after annealing with furnace 1

The stressstrain curve of tube sections after standard annealing shows an ultimate tensile strength of approximately 650 N/mm2 (Figure 4). The measured average break elongation is 45% with a standard deviation of 4.6%. The extreme minimum values for the break elongation are more than 39%. To be on the safe side, for stents with this annealing, no strut or strut section should ever experience a distortion close to or above this value.

600 stress in N/mm 400 200 0 0 10 20 strain in % 30 40

Figure 4: Stress/strain-curve after annealing with furnace 1

The results with the standard procedure of furnace 1 clearly show the necessity to improve the annealing process, especially if stents are filigreed with extremely thin struts. The main parameters for the optimisation were the time and temperature of the annealing process. Both parameters strongly influence each other. The cross section in Figure 5 illustrates the extremely fine grain size of ASTM 11 (9 m) obtained using the optimum process parameters for furnace 2. The grains are only one third the size of the grains obtained after annealing in furnace 1. With this
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extremely small grain size, higher fatigue strength can be expected [3] and the corrosion resistance will also be improved. [4] The break behaviour of the material will be different, but in general improved [5].

Figure 5: Cross Section of the grain after optimised annealing with furnace 2

Figure 6 shows a typical stressstrain curve of annealing with furnace 2. With the optimised annealing parameters the break elongation has been increased to average values of more than 50% for stents made of 1.8 x 0.14 mm tubing, which is a significant improvement. However, it must be stated here that the finest grain size does not necessarily result in the highest break elongation. A compromise had to be found during the investigation.

600

stress in N/mm

400

200

0 0 20 strain in % 40 60

Figure 6: Stress/strain-curve after annealing with furnace 2

The standard deviation of the tension test results was reduced to 2.17 %, compared with 4.6 % using furnace 1. Because reliability of the processes is essential when manufacturing medical products, this improvement is of strong significance and
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confirms that the annealing process using furnace 2 and the optimum parameters produce more stable results. Finer grain sizes typically increase tensile strength. After annealing in furnace 2, the ultimate tensile strength was raised by approximately 4 %. Another positive result of the improved annealing process with furnace 2 is the better surface of the material after testing in the tension machine. The tube surface after annealing with standard furnace 1 and tension testing is rough and looks like orange peel (Figure 7). The optimised annealing with furnace 2 results in a smooth surface after tension testing, similar to the original, unstrained surface. The better surface is of significance for fatigue strength, because smoother surfaces reduce the notch effect and crack initiation during fatigue tests. A higher fatigue strength of expanded stents can be expected [6].

after annealing with furnace 1

after annealing with furnace 2

Figure 7: Tube surfaces after straining in the tension machine

The better surface is also of significance for the electropolishing process. It makes no sense to invest considerable effort in a high quality electropolished final surface of the stent to reduce restenosis (the re-narrowing of a stent-treaded artery) (Figure 8), if the smooth surface is afterwards destroyed during dilatation in the human vessel. For stents annealed with furnace 1, strut sections with a high distortion show rough surfaces after expansion. Stents that were annealed with furnace 2, have a smooth surface after expansion.

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Recently, efforts have been undertaken worldwide to produce drug-coated stents to reduce or eliminate restenosis. The achievement of a better surface is another important benefit when applying thee coatings. First, for the active drug coatings, it reduces the risk of ablations as a result of deformations of the surface during stent expansion. Second, the possibility of cracks in passive coatings of stents, which have to prevent any contact of the 316LVM with blood in the long-term, is minimised.

Figure 8: Electropolished surface of a stent

Importance of fine grain size Until now, the investigation has concentrated on tube of 1.8 x 0.14 mm in dimension. Under normal circumstances, particularly after electropolishing, the wall thickness for coronary stents is less. The investigation revealed a decrease in break elongation after the annealing parts of a thinner wall thickness. These results show the importance of fine grain size. Figure 9 demonstrates the relationship between grain size, wall or strut dimensions and the total amount of grains on the strut. The recommended amount of 10 grains across the cross section of the strut can be achieved with the standard furnace 1 only if the strut dimensions are bigger then 200 m. Similar results were observed for the surface after straining in the tension machine. With decreasing wall thickness, the surfaces were increasingly rough when the tube had been annealed using the standard procedure with furnace 1. With the fine grain size obtained by annealing in furnace 2, the surface roughness increased only slightly after straining in the tension machine. It is particularly important to take this effect into account for newer stents made of material with higher strength and
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subsequently less wall thickness. The thinner the wall thickness of the tube or the smaller the strut dimensions, the more important it is to have a fine grain size.

WALL THICKNESS AND GRAIN SIZE

30,0 25,0
MeKo (grain size ASTM 11)

total amount of grains on wall

20,0 15,0 10,0 5,0 0,0 0,1 0,12 0,14 0,16 0,18 0,2 0,22 0,24 wall thickness / mm
recommended > 10 grains on wall

standard (grain size ASTM 8)

Figure 9: Amount of grains in the strut cross section

Finally, it can be stated that tension testing of tubes is a suitable and reliable method to inspect the results of the annealing process. Test pieces of tubes, with the same tube lot number as the laser-cut stents, have to be annealed together with the stents. The later tension test gives the exact final material properties of the stents. The test can be performed quickly and is reliable. The control of the grain size is more time and cost consuming, because cross sections are required. Providing the curve of the tension test lies in a certain range, it can be assumed that the grain size is fine and acceptable. The reverse assumption that a fine grain size automatically provides a high break elongation is not valid. Summary The annealing process is an important key step in the manufacture of high quality and reliable 316LVM stents. The methods commonly applied for verifying the outcome of the annealing process such as microhardness testing are inappropriate
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and should not be used. The tension testing of tubes, processed together with stents, provides reliable results of the final material properties of stents. During the course of the investigation the grain size was reduced significantly and the break elongation improved. The surface of the strain-tested material shows substantial improvements. All results are particularly important for thin-wall stents with filigree struts.

References 1. EN 6507-1, Metallic Materials, Vickers Hardness Test, Part 1: Test Method, 1997. 2. EN 100002 Part 1, Metallic Materials, Tensile Testing, Part 1: Method of Test, 1990. 3. H.-J.Bargel and G. Schulze, Hg. Werkstoffkunde, Fifth Edition, VDI-Verlag, Dsseldorf, Germany (1988). 4. W. Jniche et al., Verein Deutscher Eisenhttenleute. Werkstoffkunde Stahl. Band 2: Anwendungen, Springer-Verlag, Berlin, Germany (1985). 5. W. Weissbach,Werkstoffkunde und Werkstoffprfung, 14 Edition, ViewegVerlag, Wiesbaden, Germany (2002). 6. E. Hornbogen, Werkstoffe, Aufbau und Eigenschaften von Keramik-, Metall-, Polymer- und Verbundwerkstoffen., Sixth Edition, Springer-Verlag, Berlin, Germany (1994).

Dr. C. Meyer-Kobbe is President and Dipl.-Ing. Bernd H. Hinrichs is Senior R&D Engineer at MeKo Laser Material Processing, Kthe-Paulus Strasse 9-11, D-31157 Sarstedt, Germany, tel. +49 5066-7079-0, fax +49 5066-7079-99, Email: laser@meko.de, internet: www.meko.de

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