专利摘要:
The present invention relates to a method for producing a body having an osseointegrated topography formed on its surface. The method comprises the steps of a) introducing a primary body of a titanium-zirconium alloy containing 13 to 17% by weight of zirconium, b) sandblasting the primary body, and c) sandblasting the primary body with hydrochloric acid, sulfuric acid and water Etching solution is etched at a temperature above 80 ° C to obtain the body, wherein the etching is carried out for a period of at least 350 seconds.
公开号:CH713033A2
申请号:CH01238/17
申请日:2017-10-10
公开日:2018-04-13
发明作者:Habersetzer c/o Institut Straumann AG Philippe;Berner C/O Institut Straumann Ag Simon;Appert c/o Institut Straumann AG Christoph
申请人:Straumann Holding Ag;
IPC主号:
专利说明:

Description: The present invention relates to a method for producing a body with an osseointegrative topography formed on its surface. The present invention further relates to a body obtainable by said method, in particular a surgical implant or a part to be fastened on a surgical implant, in particular a dental implant or a dental implant abutment.
Dental implants are artificial tooth roots made of a biocompatible and mechanically stable material, such as titanium or ceramic. They are used in the human jaw bone and by osseointegration, i.e. the direct structural and functional connection between the bone and the implant surface. Bits, bridges or individual crowns can then be attached to the dental implant either directly or indirectly by means of an abutment in order to restore the chewing function and an aesthetic appearance.
The most common dental implants on the market are made of titanium. In order to promote rapid and strong osseointegration, the surface is preferably roughened using so-called SLA® technology, which includes sandblasting the implant surface followed by acid etching.
In addition to pure titanium, titanium alloys, in particular TiZr, TÌ6A14V (TAV) orTi6A17Nb (TAN), have been proposed as material for dental implants, in particular with regard to their biofunctionality, their low specific weight, their high tensile strength and their fatigue strength.
A particularly suitable titanium-zirconium alloy is described in WO 97/29 624, the alloy containing a zirconium content of less than 25% by weight but more than 5% by weight and having mechanical properties which are not those of -alloyed and cold-formed titanium.
The alloy according to WO 97/29 624 is hot forged and subsequently cold worked. The forging process is carried out at temperatures above 850 ° C with a subsequent rapid cooling of the alloy. Alternatively, the forging process in the area of the alpha / beta phase transition can be carried out at 770 ° C to 830 ° C.
WO 97/29 624 further discloses that the alloy in addition to titanium and zircon can have other elements, such as iron in an amount of at most 0.3 wt .-% or hafnium in an amount of at most 0.5 wt. -%. Surprisingly, further developments in the technology described in WO 97/29 624 have revealed that extraordinarily high mechanical properties can be achieved by adding iron as an alloy component to the material. In fact, the addition of iron hinders grain growth and leads to an increase in the strength of the alloy.
In addition to its mechanical properties, in particular its strength, the tendency of the implant to enter into a rapid and strong interaction with the surrounding bone tissue is of great importance for a successful implantation.
With regard to rapid and strong osseointegration, it is desirable to generate a topography on the surface of the titanium zirconium implant which is similar to the known SLA® topography on titanium implants. However, given the differences in the microstructure of a titanium-zirconium alloy compared to pure titanium, this is not an easy task.
For example, the commercially available alloys TÌ6A14V or Ti6A17Nb show a duplex microstructure, which contains two coexisting alpha and beta phases, which show different etching rates. In particular, the alpha phase dissolves faster than the beta phase, which leads to an accumulation of vanadium-rich beta phase on the surface, which in use is in close proximity to the bone.
In order to achieve a controlled and phase-oriented dissolution during the etching (comparable to the SLA® treatment on titanium), a single phase structure would be desirable.
It has been found that an almost 100% single-phase microstructure can be obtained for the high-strength titanium-zirconium alloy. For this material, a topography similar to SLA® can be achieved by sandblasting and subsequent etching of the implant surface.
However, an analysis of the titanium-zirconium surface etched according to the SLA® technology has shown that in individual aspects it still differs from a titanium surface for which the same etching parameters were used. It was also found that the amount of sandblasting material, in particular corundum, after the etching step is higher than is the case for SLA®-treated titanium implants. This finding was very surprising given the relatively high hardness of the titanium-zirconium alloy and the associated assumption that less sandblasting material tends to adhere to the surface of the alloy.
Impurities are generally considered undesirable on the implant surface, not only for the reason that they lead to a change in the chemical composition of the alloy surface, but also because, depending on the type of impurities, they have an influence on the Have total surface topography, which is one of the decisive factors for maintaining good osseointegration of the implant.
CH 713 033 A2 It is therefore of great interest to treat the surface in a manner in which there are no or only minimal amounts of impurities after the treatment.
Against this background, the object of the present invention is therefore to provide a method for producing a body made of a titanium-zirconium alloy, which has particularly good mechanical properties, in particular high strength, and which one on it Surface-shaped osseointegrative topography, the method resulting in a surface that is very similar to the known SLA® surfaces on titanium implants.
In particular, the method should make it possible to obtain a surface on which the amount of sandblasting material remaining is reduced.
[0018] The object of the present invention is achieved by the method according to claim 1. Preferred embodiments of the method are defined in the dependent claims.
[0019] According to claim 1, the invention thus relates to a method for producing a body which has an osseointegrative topography formed on its surface. In particular, the body is intended for use as a surgical implant or as a part to be fastened to a surgical implant, in particular as a dental implant or dental implant abutment.
[0020] The method of the invention comprises the steps that
a) a primary body made of a titanium-zirconium alloy containing 13 to 17% by weight of zirconium is introduced,
b) the primary body is sandblasted and
c) the sandblasted primary body is etched with an etching solution containing hydrochloric acid, sulfuric acid and water at a temperature above 80 ° C. in order to obtain the body.
According to the invention and in contrast to the established SLA © technology for titanium implants, the etching is carried out for at least 350 seconds.
As noted above, a body of particularly high strength can be obtained according to the invention. In this context, it is particularly preferred that, in addition to titanium and zirconium, the alloy also has iron as an alloy component, in particular in an amount of less than 0.05% by weight. In analogy to the SLA® technology that is applied to titanium, the titanium-zirconium alloy is sandblasted in order to obtain a macro roughness on the surface. The sandblasted primary body is then etched using an etching solution containing hydrochloric acid, sulfuric acid and water at a temperature of above 80 ° C. Due to the macroscopic single-phase structure of the specific alloy mentioned above, the etching is structure-oriented, as is the case for example with the etching of SLA®-treated titanium surfaces. There is therefore no mainly two-phase system with different dissolution rates of the phases, which would result in an accumulation of one of the two phases and thus in an asymmetrical topography.
Due to the relatively harsh conditions that must be used to achieve the desired macro-roughness, some sandblasting material remains adhering to the surface during step b). The preferred blasting parameters for step b) depend on a number of factors, for example the specific blasting method, the amount and type of blasting material and the nozzle diameter. The jet pressure used in step b) is typically at least 1.5 bar.
[0024] According to the present invention, the remaining sandblasting material is efficiently removed from the surface in step c). In this regard, it was surprisingly found that for the specific etching solution and etching temperature according to SLA® technology, an efficient removal of remaining sandblasting material is obtained if the etching time is set to at least 350 seconds. Without wishing to be bound by any theory, it is believed that prolonged etching provides a deeper depth of etching and that the removal of grains at this depth ultimately results in sandblasting material breaking away from the alloy.
It was further found that by extending the etching time to at least 350 seconds, a surface can be obtained on the titanium-zirconium alloy body which is more similar to that of the known SLA® surfaces on titanium. In the end, a body with a surface with a desired topography can be obtained by the present invention, which is at the same time free of blasting material and other residues resulting from the previous processing steps, without the need for further cleaning processes to remove remaining sandblasting material.
Nevertheless, the method of the invention can of course include a cleaning step, especially using ultrasonic cleaning and vibration.
Alternatively or in addition, a thermal shock process can be carried out for an efficient removal of particles. This method is based on the different thermal expansion coefficients of the corresponding3
CH 713 033 A2 the materials: since metal contracts more strongly than corundum at low temperatures, the thermal shock thus leads to an additional loosening of grains. Specifically, the body is preferably immersed in liquid nitrogen, especially at a temperature of approximately 77K.
In theory, an extension of the etching time contradicts the established doctrine, according to which a long etching time can result in hydrogenation phenomena which can lead to hydrogen embrittlement and thus to a decrease in the mechanical stability of the body. With this in mind, the etching is preferably performed for a period of from 350 seconds to 540 seconds, more preferably from 360 seconds to 480 seconds and most preferably from 360 seconds to 420 seconds. By restricting the upper limit of the etching time, a substantial impairment of the mechanical stability of the implant can be prevented efficiently.
As noted above, it is preferred that the alloy is substantially in the alpha phase at least in the region immediately adjacent to the surface, i.e. is present in the hexagonal-close-packed (hcp) structure. Thus, the material in this region is a single phase material that is essentially beta phase free. This allows a structure-oriented etching of the surface and ultimately that an SLAO-like topography is achieved.
It should be noted that this embodiment includes alloys that are consistently in the alpha phase, as well as alloys that include material in a core region in the beta phase, i.e. has a higher proportion of beta phases than in the region immediately adjacent to the surface.
Although the method of the invention allows efficient removal of sandblasting material adhering to the surface, it is further preferred that the sandblasting step b) is carried out in a manner to reduce the amount of sandblasting material which adheres to the surface, to reduce. This is of particular relevance with regard to the thread section of the implant, in which the risk that particles get stuck between two thread tips is particularly high. In view of this, a sandblasting material with an average particle size in the range from 0.1 mm to 0.6 mm, in particular from 0.15 mm to 0.5 mm and in the special case from 0.2 mm to 0.4 mm has proven to be particularly preferred. In particular, Al2O 3 particles with an average particle size in the range from 0.2 mm to 0.4 mm are used as sandblasting material in step b).
As mentioned, the present invention allows a surface topography to be obtained which is very similar to the known SLA® surfaces on titanium implants. In view of the well-known finding that an SLA® topography cannot be generated on the two-phase standard alloys Ti6A17Nb and TÌ6A14V, and in view of the further finding that a topography that cannot be generated when using the established SLA® technology on titanium-zirconium alloys identical to the titanium SLA® topography, which is obtained using the same process parameters, this was very surprising.
[0033] In particular, the topography obtainable by the method of the present invention can be defined by at least one of the following parameters:
i) S a , which represents the arithmetic mean deviation (arithmetic mean déviation) of the surface in three dimensions and which is in the range from 0.1 pm to 2.0 pm, preferably in a range from 0.4 pm to 1.8 pm, more preferably from 0.8 pm to 1.7 pm and most preferably from 0.9 pm to 1.5 pm;
ii) S t , which represents the maximum peak to valley height of the profile in three dimensions and more preferably in the range from 1.0 pm to 20.0 pm, preferably in a range from 3.0 pm to 18.0 pm from 4.5 pm to 13.0 pm and most preferably from 6.0 pm to 12.0 pm; and / or iii) Ssk, which represents the skewness of the profile in three dimensions and is in a range from -0.6 to 0.6, preferably from -0.4 to 0.6, more preferably from -0.3 to 0.5.
The surface parameters are known to the person skilled in the art and represent analog parameters for three dimensions to the parameters R a , R t and R sk , which are defined in EN ISO 4287 for two dimensions. In particular, the above values relate to the values, such as are available, for example, from the WinSAM software (SAM (Surface Analysis Method) for Windows), which is known to the person skilled in the art.
[0035] Alternatively or in addition to the above parameters, the topography obtainable by the method of the present invention can be further defined by:
iv) a developed surface area Sdr, which is in the range of 15% to 25%.
In that the "gold standard" SLA® topography, as is known from titanium implants, is applied to the body of the present invention from a titanium-zirconium alloy, the body combines excellent mechanical properties due to the material are obtained with the very high osseointegrative properties which are obtained at least in part due to the topography.
CH 713 033 A2 As mentioned, the mechanical properties of the titanium-zirconium alloy are extremely good. In particular, its tensile strength and its 0.2% yield strength are on average approx. 17% higher than for cold-worked titanium. In addition, the tensile strength and the 0.2% yield strength are also higher compared to ISO-standardized Ti6A17Nb. In the context of the present invention, particularly good mechanical properties were found for a titanium-zirconium alloy containing zirconium in an amount of 13 to 15% by weight.
As also mentioned above, iron is preferably contained in the alloy as an alloy component. In particular, the amount of iron contained in the alloy according to the present invention is higher than 0.001% by weight, preferably higher than 0.005% by weight, more preferably higher than 0.01% by weight. The amount of iron is preferably less than 0.05% by weight.
According to a further preferred embodiment, the alloy contains less than 0.1% by weight of hafnium. More preferably, the invention is at least approximately free of hafnium. Due to the reduction in the amount of hafnium compared to conventional alloys containing up to 0.1% by weight hafnium, any problems that may arise from the inherent radioactivity of hafnium are avoided by this embodiment, which further leads to a high level of acceptance of the material by both the dentist and the patient.
As also noted above, the amount of sandblasting material that adheres to the surface of the sandblasted primary body is substantially reduced, resulting in a surface that is at least approximately free of any remaining sandblasting material. The present invention therefore clearly differs from a method in which an attempt is made to remove the standing jet material which remains after the etching merely by rinsing. Although the present invention makes it possible to at least completely remove standing blasting material adhering to the surface, it may further be preferred to treat the sandblasted primary body after step b) and before step c) with a pickling solution containing hydrofluoric acid (HF) and nitric acid (HNO 3 ) , wherein the oxide layer natively formed on the titanium-zirconium alloy is at least partially removed. In view of this, it is further preferred that the pickling is carried out using a pickling solution containing 2% by volume HF and 10% by volume HNO 3 at room temperature for about 30 seconds. This also allows the etching time to be kept below 8 minutes, preferably below 7 minutes.
According to a further aspect, the present invention thus also relates to a method for producing a body with an osseointegrative topography formed on its surface, the method comprising the steps that
A) a primary body made of a titanium-zirconium alloy containing 13 to 17% by weight of zirconium is initially introduced, the alloy further containing iron as an alloy component in an amount of less than 0.05% by weight,
B) the primary body is sandblasted,
C) the oxide layer formed natively on the titanium-zirconium alloy is at least partially removed by treating the implant with a pickling solution containing HF and HNO 3 ; and
D) the sandblasted primary body is etched with an etching solution containing hydrochloric acid, sulfuric acid and water.
Alternatively or additionally, the temperature of the etching solution during the entire etching is preferably higher than 80 ° C, more preferably higher than 90 ° C, in order to obtain the desired surface topography within a shorter time frame, and in particular within a time frame in which none are disadvantageous Effects on the mechanical stability of the body arise.
[0043] According to an additional further aspect, the present invention further relates to a method for producing a body with an osseointegrative topography formed on its surface, the method comprising the steps that
a) a body made of a titanium-zirconium alloy containing 13 to 17% by weight of zirconium is presented, the alloy further containing iron as alloy components in an amount of less than 0.05% by weight,
ß) the body is sandblasted, and
γ) the sandblasted body is etched with an etching solution containing hydrochloric acid, sulfuric acid and water for a period of at least 300 seconds, the temperature of the etching solution being higher than 80 ° C., preferably higher than 90 ° C. throughout the etching.
According to a preferred embodiment of the invention described above and the further aspect of the present invention, according to which the temperature of the etching solution during the entire etching is higher than 80 ° C, preferably higher than 90 ° C, the sandblasted primary body immediately before step c) to a temperature
CH 713 033 A2 preheated above room temperature. Thus, the temperature drop caused by immersing the cold implant is reduced or even eliminated, which leads to a higher etching temperature and ultimately to a shorter etching time and a lower hydrogen concentration.
The body can be used as a dental implant or as a surgical non-dental implant. With regard to the applications in the non-dental area, the body can be used in particular as a knee implant, hip implant or spinal implant.
According to a particularly preferred embodiment, the body is used as a dental implant or as a part to be fastened on the dental implant, namely as a dental implant abutment.
Thanks to the extraordinarily high mechanical strength of the alloy according to the present invention, the present invention allows a high degree of freedom in the design of the implants, in particular the dental implants and dental implant abutments. The increased mechanical strength is particularly advantageous where it is clinically necessary to limit the volume of the material. In this case, the present invention allows a dental implant with a diameter of 3.5 mm or less to still meet the conditions of mechanical stability.
For aesthetic requirements, particularly for the anterior region, the present invention enables abutments with a reduced volume compared to conventional abutments. Thus, less effort is required to prevent dark translucency, for example using opaque ceramic crowns, than is the case with more voluminous abutments.
Since the high material strength of the alloy according to the present invention allows a reduction in the thickness of the implant and the abutment walls, the thread diameter of the screw required for fastening the abutment to the implant can be increased, which results in higher tightening torques and increased stiffness of the dental implant system results. Ultimately, better material fatigue values and thus a positive influence on long-term prediction can be achieved.
Examples The present invention is further illustrated by means of the following working examples.
Dental implants of a titanium-zirconium alloy containing 13 to 17% by weight of zircon were subjected to a sandblasting step followed by an etching step.
[0052] The sandblasting step was carried out using Al2O3 (corundum) particles as the sandblasting material.
For the etching, the samples were immersed in an etching bath containing hydrochloric acid, sulfuric acid and water (with a ratio of HCl (32%), H2SO4 (95%) and H20 of 2: 1: 1).
Immersion was carried out for 360 seconds before the samples were rinsed with deionized water and kept in aqueous solution for further storage.
Surface Topography The surface topography obtained by the above treatment and its similarity to the surface topography of the well-established SLA® titanium body is illustrated by means of the figures, of which:
1 shows an SEM image of the surface of the body treated according to the present invention with a scale corresponding to 10 micrometers in the lower left corner of the image; and
Figure 2 shows an SEM image of the surface of a SLA® titanium body (for comparison purposes).
As can be seen from the figures, the sample of the present invention shown in FIG. 1 shows a surface topography which is very similar to that of the known and established SLA® surface on titanium, which is shown in FIG. 2 is.
Remaining amount of sandblasting material Additional samples were analyzed using energy dispersive xray analysis (EDX) to measure the remaining amount of sandblasting material remaining on the surface after the etching step.
In the context of the EDX experiments, a first sample set (sample 1) was etched using the acid bath mentioned above for 360 seconds, while a further sample (sample 2) was etched using the same etching bath, but for 300 seconds (for comparison purposes) ).
Two corundum batches, which differ in particle size distribution and average particle size, were used for sandblasting: sand 6 was used for a first subset of samples 1 (sample 1.1)
CH 713 033 A2 sandblast using corundum particles, 85% of which have a particle size of 0.21 to 0.355 mm, the average particle size thus being in a range of 0.2 mm to 0.4 mm (sand A), while for a second Sub-set of samples 1 (sample 1.2) and comparative sample 2, sand containing corundum with a larger average particle size than sand A was used as sandblasting material (sand B).
The treatment resulted in three samples (samples 1.1, 1.2 and 2), as summarized in Table 1 below:
Table 1
Example No. 1.1 1.2 2 (comparison)
Etching time 360 seconds 360 seconds 300 seconds
Sandblasting material Sand A Sand B Sand B The Al contents (% by weight), which were detected by means of EDX, are shown in Table 2.
Table 2
Example No. 1.1 1.2 2.2
Al (% by weight) 0.1 0.5 1.3 As can be seen from Table 2, there was a significant decrease in the Al content (which indicates the amount of corundum particles adhering to the surface) for the samples 1.1. and 1.2. compared to comparative sample 2.
As is also shown in Table 2, a further decrease in the Al content and thus in the remaining corundum adhering to the surface was found for sample 1.1, which was sandblasted with sand A with an average particle size in the range from 0.2 mm to 0.4 mm compared to sand B with a larger average particle size than sand A (sample 1.2).
权利要求:
Claims (15)
[1]
claims
1. A method for producing a body with an osseointegrative topography formed on its surface, the method comprising the steps that
a) a primary body made of a titanium-zirconium alloy containing 13 to 17% by weight of zirconium is introduced,
b) the primary body is sandblasted and
c) the sandblasted primary body is etched with an etching solution containing hydrochloric acid, sulfuric acid and water at a temperature above 80 ° C. in order to obtain the body, the etching being carried out for at least 350 seconds.
[2]
2. The method of claim 1, wherein the etching is performed for a period of from 350 seconds to 540 seconds, more preferably from 360 seconds to 480 seconds and most preferably from 360 seconds to 420 seconds.
[3]
3. The method of claim 1 or 2, wherein at least in the region immediately adjacent to the surface, the alloy is substantially in the alpha phase.
[4]
4. The method according to any one of the preceding claims, wherein in step b) AÌ2O 3 particles with an average particle size of 0.1 mm to 0.6 mm, in particular from 0.15 mm to 0.5 mm and in the special case of 0 , 2 mm to 0.4 mm can be used as sandblasting material.
[5]
5. The method according to any one of the preceding claims, wherein the topography are defined by at least one of the following parameters:
i) S a , which represents the arithmetically average deviation of the surface in three dimensions and which is in the range from 0.1 pm to 2.0 pm, preferably in a range from 0.4 pm to 1.8 pm, more preferably from 0.8 pm to 1.7 pm and most preferably from 0.9 pm to 1.5 pm;
ii) S t , which represents the maximum peak-to-valley height of the profile in three dimensions and in the range from 1.0 pm to 20.0 pm, preferably in a range from 3.0 pm to 18.0 pm, more preferably from 4.5 pm to 13.0 pm and most preferably from 6.0 pm to 12.0 pm;
iii) Ssk, which represents the skewness of the profile in three dimensions and is in a range from -0.6 to 0.6, preferably from -0.4 to 0.6, more preferably from -0.3 to 0.5; and / or iv) a developed surface Sdr which is in the range from 15% to 25%.
[6]
6. The method according to any one of the preceding claims, wherein the amount of zirconium contained in the alloy is 13 to 15 wt .-%.
CH 713 033 A2
[7]
7. The method according to any one of the preceding claims, wherein the amount of iron contained in the alloy is higher than 0.001% by weight, preferably higher than 0.005% by weight, more preferably higher than 0.01% by weight.
[8]
8. The method according to any one of the preceding claims, wherein the amount of iron contained in the alloy is less than 0.05 wt .-%.
[9]
9. The method according to any one of the preceding claims, wherein the alloy contains less than 0.1 wt .-% hafnium.
[10]
10. The method according to any one of the preceding claims, wherein after step b) and before step c) the sandblasted primary body is treated with a pickling solution containing hydrofluoric acid and nitric acid, the oxide layer formed natively on the titanium-zirconium alloy being at least partially removed.
[11]
11. The method according to any one of the preceding claims, wherein the temperature of the etching solution during the entire etching is higher than 80 ° C, more preferably higher than 90 ° C.
[12]
12. The method according to any one of the preceding claims, wherein the sandblasted primary body is preheated to a temperature above room temperature immediately before step c).
[13]
13. Body available according to one of the preceding claims.
[14]
14. The body of claim 13, wherein it is a surgical implant or a part to be fastened on a surgical implant.
[15]
15. The body of claim 14, wherein it is a dental implant or a dental implant abutment.
CH 713 033 A2
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同族专利:
公开号 | 公开日
ES2786598T3|2020-10-13|
US10864062B2|2020-12-15|
EP3308808A1|2018-04-18|
EP3685865A1|2020-07-29|
US20180104026A1|2018-04-19|
EP3308808B1|2020-02-26|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2020-12-15| AZW| Rejection (application)|
优先权:
申请号 | 申请日 | 专利标题
EP16193726.3A|EP3308808B1|2016-10-13|2016-10-13|Process for preparing a body having an osseointegrative topography formed on its surface|
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