CN101466414A - Metal implants - Google Patents
Metal implants Download PDFInfo
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- CN101466414A CN101466414A CN200780021898.9A CN200780021898A CN101466414A CN 101466414 A CN101466414 A CN 101466414A CN 200780021898 A CN200780021898 A CN 200780021898A CN 101466414 A CN101466414 A CN 101466414A
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- implant
- metal structure
- ceramic coating
- silver
- hydroxyapatite
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Abstract
An implant with a metal structure for use in a surgical procedure, in which at a region of the implant to be in contact with bone the metal structure is provided with a roughened surface. The roughened region is then provided with a ceramic coating comprising hydroxyapatite by a thermal spraying process. Biocidal ions of silver are absorbed into the ceramic coating, and gradually leach out into body fluids after implantation. The hydroxyapatite enhances bone regrowth into the implant, while the silver ions suppress infection.
Description
The present invention relates to be used for the metal implant of operation process, wherein this implant will contact with bone to small part, particularly biocidal material is introduced in this implant suppressing or control infection, and the manufacture method of this implant.
Various operation processs need use implant.For example can be in prothesis by the canceration bone that replaces by metal implant removing.This implant can be a titanium alloy for example, and it is very hard and lighter.If the part of this implant will can move with respect to adjacent body part, so knownly on this part, provide smooth and polished surface; Under the part of this implant will embed situation in the bone, the known hot-spraying coating (for example US4746532) that comprises hydroxyapatite of providing was to improve the growth of bone on this implant.
The potential problems of any this implant are the risks that infects.Described in WO 2005/087982, can handle forming whole and surface layer that introduce biocidal material with this metallic matrix to the titanium implant to form.This method is included in the phosphoric acid being higher than under the voltage of 50V this time of at least 30 minutes of implant anodization, to generate surface layer, carries out ion exchange then to introduce biocidal metal ion in this surface layer.Before anodization preferably with this surface finish.Produce the hard surface coatings of titanium oxide with the anodization of particular electrolyte and certain current density, its thickness is about 0.14 μ m usually, but wherein exist diameter to be about the hole that 5 μ m and the degree of depth are about 0.4 μ m, be filled with titanium oxide (or titanium phosphate) in this hole as hydrolyzate.Can introduce silver ion then, mainly introduce in the material in these holes, so that required biocidal effect to be provided.Yet this processing mainly is applicable to the implant that comprises titanium.
According to the present invention, provide and be used for the implant that contacts with bone to small part, this implant comprises metal structure, wherein the part surface at least of this metal structure has the ceramic coating that comprises hydroxyapatite, and wherein this ceramic coating is included in the silver ion that can leach into gradually after the implantation in the body fluid.
The use of hydroxyapatite coating layer has been considered to improve the growth of bone on this implant.Silver is biocidal material.The existence demonstration of silver in coating suppressed growing into of collagen, and can not suppress growing into of bone.This part for the treatment of the implant that contacts with bone preferably has coarse surface, and it has also improved and the engaging of bone.
The present invention also provides the manufacture method that is used for the implant that contacts with bone to small part, this implant comprises metal structure, this method may further comprise the steps: the ceramic coating that will comprise hydroxyapatite by the thermal spraying of using the plasma spray coating system is deposited on the part surface at least of this metal structure and the silver ion that can leach into gradually after implantation in the body fluid is incorporated in this ceramic coating.
Silver is suitable for makes this biocidal material (biocidal material), because because the existence of chloride ion and the low-solubility of silver chloride cause it not to be dissolved in the body fluid especially.This ceramic coating is not introduced the ion of other element (for example copper, stannum, antimony, lead, bismuth, zinc or silicon).By ion exchange silver ion is introduced in this coating, and this coating after not fired, so this silver ion can leach in the body fluid after implantation gradually.
Preferred this treats that the part surface that contacts with bone at first passed through roughening and handles before applying this ceramic coating.
This ceramic coating normally white.Preferred silver ion with the color that neither changes this ceramic coating again in time lapse or be exposed to the form that does not change its color under the situation of light and exist.For example, this hydroxyapatite can comprise Ag
2HPO
4, it is white.Can use the aqueous solution of the silver ion that comprises low concentration (, but preferably being not less than 0.01mM), adsorb the ion of this biocidal material by ion exchange preferably less than 1.0mM.Alternately, in principle, can before being used to apply this implant, it in hydroxyapatite, introduce silver-colored cation, for example by contacting, perhaps by carrying out co-precipitation with required doped level with soluble silver salt; Yet the plasma spray coating step can reduce the degree that silver can leach from final coating.
For the implant of titanium-base alloy, also can be by not being higher than 20mA/cm under the voltage that the basic all surfaces of this implant structure is being higher than 50V in phosphoric acid for example
2Electric current under anodization at least 30 minutes, this surface is handled to absorb silver ion, to produce the oxide layer of the pitting that wherein has the ionic absorption material.Can mainly introduce silver ion in the material in these holes then, so that biocidal effect to be provided.Although this anodization step is not the normal method of treatment surface before this deposition of hydroxyapatite, be surprisingly found out that this hydroxyapatite and this stone oxide surface with pitting are very goodly bonding.May be more surprisingly, this hydroxyapatite coating layer can not suppress the leaching of silver ion from this anodized surface, therefore when this implant is in human body or animal body, provides biocidal effect.
At the voltage that is higher than 50V with have and carry out anodization under the condition of electric current restriction and have two kinds of effects: it has produced the fine and close hard surface layer that thickness is mainly determined by this voltage, with and on this surface, produced subsequently and be filled with that some is softer and than the shallow hole of porous materials.Use this preferred anodizing voltage, concentration of phosphoric acid preferably is at least 1M, more preferably 2～3M.The absorption of thing metal ion of killing livestock subsequently mainly enters in the material in this shallow hole, make can be by controlling this anodizing voltage size and its persistent period total amount of controlling biocidal material, with quantity and the size of controlling this shallow hole.
Anodization can be carried out to the voltage of 500V～750V at height, but preferably carries out between 50V～150V.Persistent period can reach 24 hours, but preferably is no more than 12 hours, for example 0.5 hour, 2 hours or 6 hours.Carrying out an anodized advantage under the voltage in this scope is can not have a negative impact to this surperficial fineness; If before anodization part surface is polished so that it is glossy, it still maintains gloss after the high voltage anode step so.This appears as emulsus or the anodized effect formation of lacklustre low-voltage contrast with making this surface.
Of the present invention alternative aspect, provide and be used for the implant that contacts with bone to small part, this implant comprises metal structure, wherein the whole substantially surface of this metal structure all has anodized hard surface oxide layer, the pitting that the ionic absorption material is wherein arranged, by ion exchange the ion of biocidal material is introduced in the described pitting, and wherein this metal structure have the ceramic coating that comprises hydroxyapatite to this anodized surface of small part.
The metal structure of reparation usefulness implant is the form of rustless steel, titanium alloy or cobalt/evanohm normally.The standard alloy that is used for this purpose is the titanium 90% (British standard 7252) with 6% aluminum and 4% vanadium, or chromium 26.5～30%, molybdenum 4.5～7% and residue be cobalt (British standard 7252 parts 4), but the present invention is not limited to these examples.This reparation also can be metal and the alloy thereof that comprises niobium, tantalum and zirconium with the metal structure of implant.The providing of the ionic hydroxyapatite coating layer of thing of killing livestock is provided can be applicable to this metal structure, no matter it by which kind of material is made.
Only the present invention is carried out further and more particularly description referring now to accompanying drawing in the mode of example, wherein:
Fig. 1 has shown the side view as the implant of proximal tibia prosthesis (proximal tibia prosthesis).
Implant as proximal tibia prosthesis comprises the structure of being made by titanium alloy (Ti/Al/V) 10.It is made of three parts: be used to replace the top 12 of the proximal part of tibia, 13 places are widened to form kneed lower part in the top; The lower part 14 narrower with diameter is with the respective aperture of the remainder that is arranged in tibia.To recognize that this implant structure 10 has the size of the particular patient of being specially adapted to.When implanting, the hypomere 15 on this top 13 will contact with bone, and therefore desirable is that bone should engage with the surface of this section 15.
Preferably this implant structure 10 is carried out machinery or passes through to use the polishing of electropolishing technology, so that all surface light.This surface has light gray.Carry out sandblast with the surface of this hypomere 15 of alumina powder foot couple then, use standard sandblast mask that residual surface is covered with this press polished surface of protection.Sandblast reaches the surface roughness of about Rz=4.2 μ m.Remove mask then.At first use acetone as liquid phase, use the 1M aqueous solution of sodium hydroxide that this implant structure 10 is carried out ultrasonic cleaning, rinsing in deionized water then then.
To be somebody's turn to do implant structure 10 through cleaning then is immersed in the phosphoric acid solution of stirring of 1M～5M (for example 2.1M), at maximum voltage and the 10mA/cm of 100V
2Maximum current under anodization 2 hours, to form titanium oxide and phosphatic face coat.Initial this electric current will be remarkable bigger than this easily, therefore electric current be limited; Along with form fine and close dielectric layer on this surface, this electric current is reduced under this restriction after a few minutes, should take stable low value by electric current in the remaining time of this anodizing process then.This surface forms hard surface oxide layer, because optical interference effects, it can have the outward appearance of different colours; In anodized initial period process, this surface color finally becomes redness then from purple/blueness, to blue, green, yellow, orange.Produced the film of about 0.14 μ m (140nm) thickness in the anodization of 100V.Then should be through the rinsing in deionized water once more of anodized implant structure 10.
Then this implant structure 10 is immersed in the 0.1M aqueous solution of silver nitrate of stirring, kept 2 hours.As the result of ion exchange, thereby some silver are adsorbed in this face coat.Be that at this phosphoric acid electrolyte high voltage appearance and the anodized effect of low current this surface has formed the hard anodizing oxide skin(coating) that common thickness is about 0.14 μ m, but, wherein exist general diameter to be about the hole that is filled with titanium oxide that 5 μ m and the degree of depth are about 0.4 μ m as the dissolved results of hydrolysis of local titanium.This hole planar is about circle, occupies 15～20% surface area.Surface analysis technique confirms that the silver of absorption is mutually relevant with the titanium oxide/phosphate of this surface after ion-exchange treatment.Silver little degree be adsorbed onto on the outer surface of this hard formation, and be adsorbed onto largely in this hole than the porous material internal.
Therefore be to produce the oxide skin(coating) that its thickness depends on the hard compactness of voltage (its pass is about 1.4nm/ volt) in 2 hours effect of 100V anodization, this film has the coloured appearance of being determined by film thickness, and keep this surperficial micro structure (in some parts,, being coarse fineness) in remainder for the fineness of polishing.There is pit on this surface on micro-scale, this does not influence outward appearance.This anodized surface can have at 0.1～20 μ g/cm in load
2In the scope, be generally about 5～9 μ g/cm
2Silver.
On all glossiness surfaces, cover this implant structure 10 until the about 50mm in the edge of this glossy part then with the woven resistant glass fiber torrid zone, use the wide native silver bar of 100mm to cover on the edge of this glossy part then, this paper tinsel partly covers this glass fiber tape.With nickel foil it is covered (being used for being reduced in the risk of damage of processing procedure) then.By the rough surface of plasma spray coating, be coated to the thickness of about 80 μ m then with hydroxyapatite coating (this section 15).This paper tinsel guarantees that hydroxyapatite does not deposit on this glossy surface, and the ultraviolet radiation of guaranteeing plasma generation can this glossy surface of irradiation, and it may reduce the absorption of ion to metal; Rough surface does not have such problem, because sedimentary hydroxyapatite itself is protected it.
Remove mask then, use isopropyl alcohol implant to be carried out last ultrasonic clean as solvent.Prepare to be used for the patient then.Be surprisingly found out that this hydroxyapatite and this hard oxide skin(coating) adhere finely; And can not stop after the implantation silver ion body fluid around leaching into from this anodization layer gradually at the hydroxyapatite coating layer on this rough surface, any antibacterial that makes in the implant close vicinity all is killed.Therefore suppressed the infection that this implant produces.And the coating of hydroxyapatite has improved the growth of bone on this implant.This hydroxyapatite is a white coating.
After the deposited hydroxyl apatite coating, this hydroxyapatite coating layer is impregnated in the weak solution (for example 0.33mM of silver nitrate (0.00033M) aqueous solution) of silver salt.Preferably, use deionized water to prepare this solution.Under the silver ion of like this low concentration, there is limited degree with the ion exchange of hydroxyapatite, generate the Ag of white
2HPO
4For example, have been found that the silver-colored load capacity in the hydroxyapatite coating layer is 5.9 μ g/cm after 20 ℃ flood 2 hours
2This silver load capacity raises along with the rising of silver concentration in the solution, for example uses the 0.5mM silver nitrate solution, and the silver-colored load capacity after 20 ℃ flood 2 hours is about 22.9 μ g/cm
2And use the 1.0mM silver nitrate solution, silver-colored load capacity is about 48.4 μ g/cm under identical condition
2If required load capacity is 5～10 μ g/cm
2, can use the solution of about 0.3mM～0.4mM to realize so.Found through experiments silver-colored load capacity P (μ g/cm
2) with this solution in silver concentration C (molar concentration) join by following dependence among equations:
log?P＝(1.334×log?C)+5.5
Logarithm wherein is the end with 10.
The adsorbance of silver also be can't help temperature appreciable impact (at least for the temperature in the environmental field), also can't help the dip time appreciable impact, at least at least 0.5 hour dipping.Above-mentioned 2 hours dipping has been found that the absorption that causes about 5%～15% silver ion in the solution.
If the concentration of silver nitrate solution is up to 1mM, there is light discolouration in white hydroxyapatite surface so.If under the same conditions this hydroxyapatite coating layer is immersed in the 10mM silver nitrate solution, owing to generated silver phosphate, so the surface becomes light yellow; Find that in this case silver-colored load capacity is about 555 μ g/cm
2This silver-colored load capacity is higher than the desirable value of the gratifying biocidal properties of this implant; Yellow color does not have captivation yet; And if existence is exposed to the risk (because the silver ion photo-reduction is a silver) that this surface of light will become ash.
With recognizing that no matter which kind of metal the metal of this structure may be, can as mentioned above silver ion be incorporated in the hydroxyapatite.This hydroxyapatite can be coated on the anodized titanium (as mentioned above), perhaps is coated on non-anodized titanium or cochrome or any metal that other is fit to.
In the variant of aforesaid whole process, with the anodization of titanium implant so that the surface with ion exchange character to be provided; Apply this surperficial roughening part with hydroxyapatite then; Using then is enough to all provide greater than 2 μ g/cm on this hydroxyapatite coating and uncoated part
2The concentration of silver ions of load capacity, the treated part with uncoated that this surperficial hydroxyapatite applies is carried out ion exchange.
(the preferred negative carrying capacity is no more than 30 μ g/cm in hydroxyapatite coating layer
2) and in the surface of this metal implant, provide silver-colored load capacity to increase to be used in implantation after leach into silver in the body fluid, therefore improved the biocidal properties of this implant.
After in being implanted to body, silver ion leaches into from this hydroxyapatite coating layer in the adjacent body fluid gradually, has therefore guaranteed biocidal effect.Have been found that leaching rate is subjected to the control of the dissolubility of silver chloride.Use has been carried out experiment test at the hydroxyapatite coating layer of the structural load silver of cochrome, is immersed in the 500ml 0.9% NaCl aqueous solution that keeps stirring, and keeps 2 time-of-weeks at 35 ℃.
Take out the 50ml sample every day and analyze, and replace (for example being illustrated in the joint replacement gradually of synovial membrane fluid (sinovial fluid) on every side) with fresh NaCl solution.In this embodiment, the amount of initial silver is about 60 μ g/cm
2(twice that is about maximum desired level).In the whole process of experiment, the silver concentration in this solution that records keeps about 0.4～0.6ppm; This is consistent with expectation concentration (it can be 0.48ppm (silver)) based on the dissolubility of silver chloride.Therefore will be in the biocidal effect effective time of meeting after the implantation by controlled (it is reducing about 16% in two weeks in above-mentioned experiment) from the loss speed and the initial silver-colored load capacity of the body fluid around the implant surgery location.
Claims (13)
1. be used for the implant that contacts with bone to small part, this implant comprises metal structure, wherein the part surface at least of this metal structure has the ceramic coating that comprises hydroxyapatite, and wherein this ceramic coating comprises the silver ion that can leach into gradually in the body fluid after implantation.
2. the implant of claim 1, if the master metal titanium of this metal structure wherein, the surface of this metal structure has hard oxide surface, and the pitting of ionic absorption material is wherein arranged.
3. claim 1 or 2 implant, wherein this implant treat the part that contacts with bone have with than the coarse surface of metal structure, this rough surface has this ceramic coating.
4. each implant in the aforementioned claim, wherein the load capacity of silver ion in this ceramic coating is 0.1～30 μ g/cm
2
5. the manufacture method that is used for the implant that contacts with bone to small part, this implant comprises metal structure, this method may further comprise the steps: the ceramic coating that will comprise hydroxyapatite by the thermal spraying of using the plasma spray coating system is deposited on the part surface at least of this metal structure and the silver ion that can leach into gradually after implantation in the body fluid is incorporated in this ceramic coating.
6. the method for claim 5 is if the master metal titanium of this metal structure wherein before this ceramic coating deposition, to produce hard oxide surface, wherein has the pitting of ionic absorption material by this metal structure of anodization.
7. claim 5 or 6 method also are included in before this ceramic coating deposition, and the part surface at least of this metal structure is handled through roughening.
8. each method in the claim 5～7, wherein the load capacity of silver ion in this ceramic coating is 0.1～30 μ g/cm
2
9. each method in the claim 5～8 wherein by the implant through applying is impregnated in the solution that comprises silver ion, is incorporated into silver ion in this sedimentary ceramic coating by ion exchange.
10. the method for claim 9 wherein uses the aqueous solution of the concentration of silver ions that comprises 0.00001M～0.001M to carry out ion exchange with this ceramic coating.
11. each method in the claim 5～10 wherein in thermal spray process, at first will not have the part surface of this ceramic coating with this metal structure of masked that combines tinsel.
12. implant by each described method manufacturing in the claim 5～11.
13. be used for the implant that contacts with bone to small part, this implant comprises metal structure, wherein the whole substantially surface of this metal structure all has anodized hard surface oxide layer, the pitting that the ionic absorption material is wherein arranged, by ion exchange the ion of biocidal material is introduced in the pitting of described ionic absorption material, and wherein this metal structure have the ceramic coating that comprises hydroxyapatite to this anodized surface of small part.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0611437.5 | 2006-06-12 | ||
| GB0611437A GB0611437D0 (en) | 2006-06-12 | 2006-06-12 | Metal implants |
| GB0700713.1 | 2007-01-15 | ||
| GB0700713A GB0700713D0 (en) | 2007-01-15 | 2007-01-15 | Metal implants |
| PCT/GB2007/050327 WO2007144667A2 (en) | 2006-06-12 | 2007-06-11 | Metal implants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101466414A true CN101466414A (en) | 2009-06-24 |
| CN101466414B CN101466414B (en) | 2013-05-08 |
Family
ID=36745603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780021898.9A Expired - Fee Related CN101466414B (en) | 2006-06-12 | 2007-06-11 | Metal implants |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN101466414B (en) |
| ES (1) | ES2358228T3 (en) |
| GB (1) | GB0611437D0 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102525672A (en) * | 2010-12-29 | 2012-07-04 | 北京汇福康医疗技术有限公司 | Oral implant abutment and manufacture method thereof |
| CN105559948A (en) * | 2015-12-14 | 2016-05-11 | 北京大学第一医院 | Artificial joint prosthesis |
| CN112088019A (en) * | 2018-05-07 | 2020-12-15 | 沃尔德马连接两合公司 | Antimicrobial implant coating |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH694935A5 (en) * | 2000-07-26 | 2005-09-30 | Straumann Holding Ag | Oberflaechenmodifizierte implants. |
| GB0405680D0 (en) * | 2004-03-13 | 2004-04-21 | Accentus Plc | Metal implants |
-
2006
- 2006-06-12 GB GB0611437A patent/GB0611437D0/en not_active Ceased
-
2007
- 2007-06-11 ES ES07733748T patent/ES2358228T3/en active Active
- 2007-06-11 CN CN200780021898.9A patent/CN101466414B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102525672A (en) * | 2010-12-29 | 2012-07-04 | 北京汇福康医疗技术有限公司 | Oral implant abutment and manufacture method thereof |
| CN102525672B (en) * | 2010-12-29 | 2015-03-11 | 北京汇福康医疗技术有限公司 | Oral implant abutment and manufacture method thereof |
| CN105559948A (en) * | 2015-12-14 | 2016-05-11 | 北京大学第一医院 | Artificial joint prosthesis |
| CN105559948B (en) * | 2015-12-14 | 2018-12-18 | 北京大学第一医院 | A kind of artificial joint prosthesis |
| CN112088019A (en) * | 2018-05-07 | 2020-12-15 | 沃尔德马连接两合公司 | Antimicrobial implant coating |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2358228T3 (en) | 2011-05-06 |
| GB0611437D0 (en) | 2006-07-19 |
| CN101466414B (en) | 2013-05-08 |
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