CN105496577A - Titanium implant with bone resorption lacunae-like surface appearance and preparation method of titanium implant - Google Patents

Titanium implant with bone resorption lacunae-like surface appearance and preparation method of titanium implant Download PDF

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CN105496577A
CN105496577A CN201510915424.5A CN201510915424A CN105496577A CN 105496577 A CN105496577 A CN 105496577A CN 201510915424 A CN201510915424 A CN 201510915424A CN 105496577 A CN105496577 A CN 105496577A
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titanium implant
titanium
implant
pit
preparation
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CN105496577B (en
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田卫东
谢利
郭维华
霍芳军
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Sichuan University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
    • A61C8/0018—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the shape
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon

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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Dentistry (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Prostheses (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a titanium implant with a bone resorption lacunae-like surface appearance and a preparation method of the titanium implant. The preparation method comprises the steps of adopting a mixed solution of formate/acetate as electrolyte, wherein formate ion concentration is within the range of 0.05 to 10mol/L, acetate ion concentration is within the range of 0 to 2.4mol/L. Adopting a stepped current rising mode to perform anodic oxidation treatment on the titanium implant, wherein an initial current density value is set as 2.5 to 10mA/cm<2> after electrifying, the value gradually rises, each step is kept for 1 to 10min, a current rising progression value is 2.5 to 10mA/cm<2>, a fixed current rising progression value and keeping time are treated every time, the step number is 5 to 20, and the current-time curve is in the shape of up-going step. By using the method, a micron lacunae structure similar to the bone resorption lacunae in configuration and three-dimensional size can be prepared on the surface of the titanium implant. A cytobiology assessment result shows that the titanium implant with the bone resorption lacunae-like surface appearance prepared by the invention can remarkably promote an osteoblast function.

Description

There is titanium implant and the preparation method of similar Bone resoiption pit surface topography
Technical field
The invention belongs to oral cavity titanium implant surface processing technology field, relate to a kind of titanium implant and the preparation method with imitative Bone resoiption pit body structure surface pattern.
Background technology
Tooth-planting treatment has become the treatment means that clinical oral Anodontia repair is best now.The surface nature of implantation body affects one of most important factor of its Integrated implant performance, and therefore, the process for treating surface of implantation body is also the key element affecting implantation body's product quality.Although the implant system used clinically at present have employed a variety of implant surface treatment technology, the requirement of general planting treatment can be met.But run into the situation that some patient self alveolar bone sclerotin bone amount is not good, or the therapeutic modality that immediate implant Immediate prosthesis etc. is emerging, just the Integrated implant ability of implantation body is had higher requirement.Therefore, research and development can improve one of the Integrated implant speed of implantation body and the novel surface treatment technology primary study direction becoming implantation body field of intensity further.
The process for treating surface of implantation body has a lot of methods, physics, chemistry, biological etc., by these methods, the change of implant surface pattern, surface chemical composition and surface energy can be brought.Wherein, surface topography is one of important factor.Different surface treatment methods can obtain the surface topography of great disparity; as groove; rough irregular surface structure; micropore or bowl configurations; [the DavidM such as nano-particle or nano tube structure; EhrenfestD; CoelhoPG; KangBS; SulYT; AlbrektssonT.Classificationofosseointegratedimplantsurfa ces:materials.chemistryandtopography.TrendsinBiotechnolo gy, 2010,28 (4): 198 ~ 206].Does is it the most favourable which type of surface topography form Integrated implant to implantation body?
In recent years, academia proposes bionic theory.Research shows, the forming process at implantation body-synosteosis interface and the similar of naturally new and old synosteosis interface.Natural bone is formed or in process of reconstruction, the formation of absorption lacuna structure to new and old synosteosis interface that osteoclast is formed at old bone surface bone resorption has important function.Therefore, J.E.Davies etc. think that optimal implantation body should have the topological surface topography of similar Bone resoiption pit structure.Bone resoiption pit, also referred to as Hao Fusi lacuna (Howship ' slacunae), in cellular or nibble the lacuna spline structure of shape, sum up document to the description of Bone resoiption pit, characterization data, absorption lacuna has following shape characteristic: 1. the profile of absorption lacuna and edge clear can be distinguished, with do not absorb surface of bone and demarcate clear, as the pit of downward " excavating " on level land.2. the pattern of single absorption lacuna is subcircular or avette, and multiple absorption lacuna is got together, and also presents channel form, but the contour line of absorption lacuna is level and smooth.Size characteristic: the length and width footpath of absorption lacuna is distributed in several micron to dozens or even hundreds of micron, the degree of depth can reach several micron to tens microns.As can be seen here, Bone resoiption pit has distinct shape characteristic.
Have some technical methods can prepare pit shape structure at titanium implant surface both at home and abroad, conventional method is blasting treatment.The SLA surface implant having of Straumann house journal, diameter is prepared in the micron bowl configurations of 30 ~ 100 μm and the pit structure of 1 ~ 3 μm in implant surface by the method for sandblasting acid etching, the principle of sandblasting is, under certain air pressure, white fused alumina, titanium oxide, SiC granule, corundum are ejected into implant surface, forms pit shape structure under the shock of sand grains.Sand grains particle diameter is larger, and air pressure is larger, and diameter and the degree of depth of pit are larger.The principle of acid etching is the corrosiveness utilizing the acid solutions such as sulphuric acid, hydrochloric acid, Fluohydric acid., reacts, titanium is dissolved with titanium, because surperficial zones of different is by the degree varies sample dissolved, thus form pit shape structure, acid etching can with sandblasting coupling, also can implement separately.Sandblasting: blur margin is clear, the degree of depth is inadequate.
The Chinese patent CN200510062209.1 that can obtain open a kind of " having the method for bioactivity, porous structure in the preparation of pure-titanium tooth implantation surface ", under employing corundum sandblasting 4bar pressure, the method for sandblasting constructs the micron order pit that diameter is 10 ~ 30 μm.The bowl configurations formed is dimensionally with in the size range of Bone resoiption pit, but shape exists notable difference, and its shape is irregular, irregularly shaped relevant with grit blast.
Chinese patent CN201210052274.6 open a kind of " preparing the method for two-stage micron-submicron microstructure at titanium alloy dental implant surface ", is consisting of HCl88-110g/L, HF39-63g/L, NH 4adopt the method process titanium implant of electrolytic etching in the electrolyte of F10-25g/L, prepare the micron order micro-structure surface of diameter 2-5 μm.But micron bowl configurations size prepared by this method is less than normal compared with absorption lacuna.Zhao etc. utilize electrochemistry micro Process method to have controlled dimensions (10 at titanium surface construction, 30,100 μm) regularly arranged micron bowl configurations, but this method is only suitable for preparing the smooth titanium sheet of profile rule, is not suitable for screw-shaped titanium implant product.
Chinese patent CN201210232397.8 discloses a kind of method of anatase titanium dioxide rete of the micrometer/nanometer multistage composite pore structure formed on this titanio basal surface.Adopt sulphuric acid and hydrochloric acid mixed solution to carry out acid etch process, after acid etch process, form micrometer grade hole structure at described titanio basal surface, then carry out anodized, electrolyte is 0.3wt%NH 4f+0.2wt%H 2o 2ethylene glycol solution on micron scale construction, form nano grade pore structure, namely form micrometer/nanometer multistage composite pore structure; Heat-treat, after Overheating Treatment, form the anatase titanium dioxide rete of micrometer/nanometer multistage composite pore structure at titanium substrate material surface.The aperture of micron openings is 2-6 μm, and the aperture of nano-pore is 10-100nm.Compare Bone resoiption pit micron openings aperture obvious much little.In sum, domestic and international existing patented technology method all can not prepare similar Bone resoiption pit loose structure at titanium implant surface.
Summary of the invention
In order to solve above technical problem, the invention provides and a kind of there is titanium implant of imitative Bone resoiption pit body structure surface pattern and preparation method thereof.
Solve a kind of titanium implant with similar Bone resoiption pit body structure surface pattern in the present invention of above technical problem, it is characterized in that: comprise titanium implant body and pit layer, the pit of described pit layer is for nibbling shape or cellular, shape profile is tied similar with three-dimensional dimension to the osteoclast absorption lacuna that bone resorption is formed on surface of bone, and similarity can be 96-100%.
Described pit major diameter is 2-80 μm, and wide footpath is 2-40 μm, and the degree of depth is 2-40 μm.
Described titanium implant body is titanium implant or titanium sheet.
A kind of method preparing the titanium implant with similar Bone resoiption pit body structure surface pattern in the present invention, is characterized in that:
Comprise the following steps:
(1) pretreatment: by titanium implant cleaning treatment, stand-by after dry in baking oven, baking temperature 50-70 DEG C, time 20-60min; For greasy dirt and the impurity of eccysis titanium implant surface.
(2) electrolyte quota: preparation formates/acetate mixed electrolytic solution, the molar concentration of formate ion is 0.05 ~ 10mol/L, and the molar concentration of acetate ion is 0 ~ 2.4mol/L;
The kind of electrolyte and consumption have a great impact the formation of the loose structure of the oxide-film that surface of metal titanium is formed and character tool, formate ion and acetate ion have special field-enhanced dissolution effect to titanium oxide, the main cause and the essential condition that form pit shape structure, the composition of anodic oxidation electrolyte and concentration determine the shape facility of the loose structure of obtained anode oxide film, adopt containing the electrolyte prescription of these two kinds of ions under same electrical quantity condition, cannot obtain prepare in the present invention analogous shape, size bowl configurations.
(3) anodic oxidation device: take adjustable D. C regulated as anodic oxidation power supply, titanium implant in step (1) is connected as anode with positive source, face of cylinder hollow cathode is made with titanium foil or stainless steel foil, be connected with power cathode as negative electrode around titanium implant, again by pending for titanium implant partially submerged enter under liquid level, electrolyte in step (2) is placed in electrolysis bath, magnetic agitation; Electrolysis bath can be glass or lucite electrolysis bath.
Each zone current Density Distribution of the effect Shi Shi implantation body of cylindrical cathode is substantially even, and the effect of magnetic agitation is that electrolyte in course of reaction is stirred.
(4) anodized: after energising, initial current density values is set to 2.5-10mA/cm2, progressively raise, often walking the retention time is 1-10min, up-flow goes forward one by one value for 2.5-10mA/cm2, each process is fixed up-flow and is gone forward one by one value and retention time, step number of passes 5-20, current-time curvel is up step;
Anodized progressively flow mode after energising: can adopt staged flow mode, often step keeps the regular hour, and current-time curvel is up step.
The effect of staged flow mode is for the field-enhanced dissolution effect of acid ion provides suitable electric field power and necessary dissolution time.
(5) post processing: the titanium implant again in ultrasonic cleaning step in deionized water (4), dry, baking temperature is 50-70 DEG C, time 20-60min, and the titanium implant namely obtained has the surface topography of similar Bone resoiption pit structure.
The effect of ultrasonic cleaning is precipitation or impurity substances that eluting remains in titanium implant surface, reaches the effect of clean implant surface.
Formates described in step (2) be sodium formate, potassium formate or ammonium formate one or more, acetate be sodium acetate, potassium acetate or ammonium acetate one or more.
Electrolyte prescription is mainly neutral salt solution, non-volatile, can preserve for a long time, stable, nontoxic, environmentally friendly, with low cost, is beneficial to and realizes commercial production.During configuration high concentration electrolyte, need the reagent that Selective dissolution degree is enough large.
Described in step (3), the distance of anode and negative electrode is 3-5cm.
Controlling described electrolyte temperature in step (3) is 10 DEG C-30 DEG C, and the formation speed of temperature on field-enhanced dissolution speed and oxide layer all has impact, temperature too low or too high time, cannot implementation result be obtained.
In the present invention, titanium implant is after preparation, the bowl configurations that implant surface is a large amount of as seen, in nibbling shape or cellular, its edge clear, demarcate clear with flat site, shape profile and the three-dimensional dimension absorption lacuna structure that all bone resorption is formed on surface of bone to osteoclast is similar.
The titanium implant of what arbitrary described method prepared above have imitative Bone resoiption pit body structure surface pattern all belongs to protection scope of the present invention.All features disclosed in this description, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this description (comprising any accessory claim, summary), unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
Accompanying drawing explanation
Fig. 1 is titanium implant scanning electron microscopic observation figure in embodiment 1 in the present invention
Fig. 2 A-2E is the micron pit morphological analysis figure on class Bone resoiption pit surface in the present invention
Wherein A is that micron pit SEM schemes; B is that micron pit profile detects figure automatically; C is micron pit major diameter cartogram; D is micron pit wide footpath cartogram; E is micron pit area cartogram
The biological evaluation result of class Bone resoiption pit topographical surface (M) and sandblasting acid etching (SLA) and conventional anodization (S) surface sample in Fig. 3 A-3F the present invention
Detailed description of the invention
Following embodiment is convenient to understand the present invention better, but does not limit the present invention.Experimental technique in following embodiment, if no special instructions, is conventional method.Titanium transplanting body body used in following embodiment and test material, if no special instructions, be and purchase available from routine biochemistry reagent suppliers.
A kind of titanium implant with similar Bone resoiption pit body structure surface pattern in the present invention, comprise titanium implant body and pit layer, the pit of described pit layer is for nibbling shape or cellular, shape profile is tied similar with three-dimensional dimension to the osteoclast absorption lacuna that bone resorption is formed on surface of bone, and similarity can be 96-100%.Pit major diameter is 2-80 μm, and wide footpath is 2-40 μm, and the degree of depth is 2-40 μm, and titanium implant body is titanium implant or titanium sheet.
Below in conjunction with instantiation, do invented process and further elaborate, specific embodiment is as follows:
Embodiment 1:
(1) pretreatment: machining or 3D are printed the titanium implant acetone manufactured, dehydrated alcohol, and deionized water is ultrasonic cleaning 5min respectively, washes away greasy dirt and the impurity on surface; Dry in an oven again, baking temperature 50 DEG C, time 30min.
(2) electrolyte: be electrolyte with sodium formate and sodium acetate trihydrate, preparation is 0.7mol/L containing formate ion concentration, and acetate ion concentration is the electrolyte of 0.3mol/L.
(3) anodic oxidation device: with D.C. regulated power supply WYJ-300V3A (Shanghai is Electrical Appliances Co., Ltd with all strength) for anodic oxidation power supply, pretreated titanium implant is connected as anode with positive source, the titanium foil of 500 × 80 × 0.1mm is curved and to be cylindricly connected with power cathode as negative electrode around titanium implant, the distance of anode and negative electrode is 3cm, by pending for implantation body partially submerged enter under liquid level, the electrolyte of preparation is placed in 500mL glass beaker, beaker is placed in heat-collecting magnetic stirring device, setting bath temperature is 25 DEG C.
(4) anodized: adopt the pattern of progressively up-flow to carry out anodized after energising, first step current density value is set to 5mA/cm 2, progressively raise, often walk and all keep 2min, up-flow value of going forward one by one is 5mA/cm 2, step number of passes 10, therefore total reaction time is 20min.
(5) post processing: after anodized, is placed in deionized water by titanium implant, ultrasonic cleaning 2min, then dries sample in an oven, baking temperature 70 DEG C, time 60min.
Adopt scanning electron microscopic observation implant surface pattern, there is a large amount of bowl configurations in titanium implant surface, bowl configurations major diameter is about 2-68 μm, and wide footpath is about 2-38.4 μm, and depth bounds is about 2-38 μm.
Embodiment 2
(1) pretreatment: machining or 3D are printed the titanium implant petroleum ether manufactured, dehydrated alcohol, and deionized water is ultrasonic cleaning 5min respectively, washes away greasy dirt and the impurity on surface; Dry in an oven again, baking temperature 70 DEG C, time 20min.
(2) electrolyte: be raw material with ammonium formate and potassium acetate, preparation is 0.7mol/L containing formate ion concentration, and acetate ion concentration is the electrolyte of 0.5mol/L.
(3) anodic oxidation device: with D.C. regulated power supply WYJ-300V1A (Shanghai is Electrical Appliances Co., Ltd with all strength) for anodic oxidation power supply, pretreated titanium implant is connected as anode with positive source, the titanium foil of 500 × 80 × 0.1mm is curved and to be cylindricly connected with power cathode as negative electrode around titanium implant, the distance of anode and negative electrode is 4cm, by pending for implantation body partially submerged enter under liquid level, the electrolyte of preparation is placed in glass beaker, beaker is placed in cryogenic thermostat bath, setting bath temperature is 20 DEG C.
(4) anodized: adopt the pattern of progressively up-flow to carry out anodized after energising, first step current density value is set to 2.5mA/cm 2, progressively raise, often walk and all keep 5min, up-flow value of going forward one by one is 5mA/cm 2, step number of passes 10.Therefore total reaction time is 50min.
(5) post processing: after anodized, is placed in deionized water by titanium implant, ultrasonic cleaning 3min, then dries sample in an oven, baking temperature 50 DEG C, time 30min.
Adopt scanning electron microscopic observation implant surface pattern, there is a large amount of bowl configurations in titanium implant surface, bowl configurations major diameter is about 2-40 μm, and wide footpath is distributed in 2-24 μm of scope, and depth bounds is about 2-26 μm.
Embodiment 3
(1) pretreatment: titanium implant acetone, dehydrated alcohol, deionized water is ultrasonic cleaning 5min respectively, washes away greasy dirt and the impurity on surface; Dry in an oven again, baking temperature 60 DEG C, time 30min.
(2) electrolyte: be raw material with sodium formate and sodium acetate, preparation is 10mol/L containing formate ion concentration, and acetate ion concentration is the electrolyte of 2.4mol/L.
(3) anodic oxidation device: with D.C. regulated power supply WYJ-200V1A (Shanghai is Electrical Appliances Co., Ltd with all strength) for anodic oxidation power supply, pretreated titanium implant is connected as anode with positive source, the titanium foil of 500 × 80 × 0.1mm is curved and to be cylindricly connected with power cathode as negative electrode around titanium implant, the distance of anode and negative electrode is 5cm, by pending for implantation body partially submerged enter under liquid level, the electrolyte of preparation is placed in 500mL glass beaker, beaker is placed in heat-collecting magnetic stirring device, setting bath temperature is 25 DEG C.
(4) anodized: adopt the pattern of progressively up-flow to carry out anodized after energising, first step current density value is set to 10mA/cm 2, progressively raise, often walk and all keep 2min, up-flow value of going forward one by one is 5mA/cm 2, step number of passes 10.Therefore total reaction time is 20min.
(5) post processing: after anodized, is placed in deionized water by titanium implant, ultrasonic cleaning 4min, then dries sample in an oven, 60 DEG C of times of baking temperature, time 40min.
Adopt scanning electron microscopic observation implant surface pattern, there is a large amount of bowl configurations in titanium implant surface, bowl configurations major diameter is about 2-50 μm, and wide footpath is distributed in 2-30 μm of scope, and depth bounds is about 2-30 μm.
Embodiment 4
(1) pretreatment: titanium implant acetone, dehydrated alcohol, deionized water is ultrasonic cleaning 5min respectively, washes away greasy dirt and the impurity on surface; Dry in an oven again, baking temperature 65 DEG C, time 25min.
(2) electrolyte: be raw material with sodium formate, preparation is the electrolyte of 0.05mol/L containing formate ion concentration.
(3) anodic oxidation device: with D.C. regulated power supply WYJ-300V3A (Shanghai is Electrical Appliances Co., Ltd with all strength) for anodic oxidation power supply, pretreated titanium implant is connected as anode with positive source, the titanium foil of 500 × 80 × 0.1mm is curved and to be cylindricly connected with power cathode as negative electrode around titanium implant, the distance of anode and negative electrode is 3.5cm, by pending for implantation body partially submerged enter under liquid level, the electrolyte of preparation is placed in 500mL glass beaker, beaker is placed in heat-collecting magnetic stirring device, setting bath temperature is 25 DEG C.
(4) anodized: adopt the pattern of progressively up-flow to carry out anodized after energising, first step current density value is set to 5mA/cm 2, progressively raise, often walk and all keep 10min, up-flow value of going forward one by one is 5mA/cm 2, step number of passes 20.Therefore total reaction time is 200min.
(5) post processing: after anodized, is placed in deionized water by titanium implant, ultrasonic cleaning 2min, then dries sample in an oven, baking temperature 55 DEG C, time 60min.
Adopt scanning electron microscopic observation implant surface pattern, there is a large amount of bowl configurations in titanium implant surface, bowl configurations major diameter is about 2-25 μm, and wide footpath is distributed in 2-15 μm of scope, and depth bounds is about 2-15 μm.
Embodiment 5
(1) pretreatment: titanium implant acetone, dehydrated alcohol, deionized water is ultrasonic cleaning 5min respectively, washes away greasy dirt and the impurity on surface; Dry in an oven again, baking temperature 55 DEG C, time 30min.
(2) electrolyte: be raw material with sodium formate and sodium acetate, preparation is 5mol/L containing formate ion concentration, and acetate ion concentration is the electrolyte of 1mol/L.
(3) anodic oxidation device: with D.C. regulated power supply WYJ-200V1A (Shanghai is Electrical Appliances Co., Ltd with all strength) for anodic oxidation power supply, pretreated titanium implant is connected as anode with positive source, the titanium foil of 500 × 80 × 0.1mm is curved and to be cylindricly connected with power cathode as negative electrode around titanium implant, the distance of anode and negative electrode is 4cm, by pending for implantation body partially submerged enter under liquid level, the electrolyte of preparation is placed in 500mL glass beaker, beaker is placed in heat-collecting magnetic stirring device, setting bath temperature is 30 DEG C.
(4) anodized: adopt the pattern of progressively up-flow to carry out anodized after energising, first step current density value is set to 5mA/cm2, progressively raises, and often walks and all keeps 2min, up-flow value of going forward one by one is 5mA/cm2, step number of passes 10.Therefore total reaction time is 20min.
(5) post processing: after anodized, is placed in deionized water by titanium implant, ultrasonic cleaning 4min, then dries sample in an oven, baking temperature 65 DEG C, time 30min.
Adopt scanning electron microscopic observation implant surface pattern, there is a large amount of bowl configurations in titanium implant surface, bowl configurations major diameter is about 2-80 μm, and wide footpath is distributed in 2-40 μm of scope, and depth bounds is about 2-35 μm.
Embodiment 6
(1) pretreatment: diameter 15mm, the pure titanium sheet of the trade mark TA1 of thickness 1mm uses acetone, dehydrated alcohol after sanding and polishing, and deionized water is ultrasonic cleaning 5min respectively, washes away greasy dirt and the impurity on surface; Dry in an oven again, baking temperature 70 DEG C, time 25min.
(2) electrolyte: be raw material with sodium formate and sodium acetate, preparation is 0.7mol/L containing formate ion concentration, and acetate ion concentration is the electrolyte of 0.3mol/L.
(3) anodic oxidation device: with D.C. regulated power supply WYJ-200V1A (Shanghai is Electrical Appliances Co., Ltd with all strength) for anodic oxidation power supply, pretreated titanium sheet is connected as anode with positive source, the titanium foil of 500 × 80 × 0.1mm is curved and to be cylindricly connected with power cathode as negative electrode around titanium implant, the distance of anode and negative electrode is 4cm, under titanium sheet is submerged into liquid level, the electrolyte of preparation is placed in 500mL glass beaker, beaker is placed in heat-collecting magnetic stirring device, setting bath temperature is 20 DEG C.
(4) anodized: adopt the pattern of progressively up-flow to carry out anodized after energising, first step current density value is set to 5mA/cm2, progressively raises, and often walks and all keeps 2min, up-flow value of going forward one by one is 5mA/cm2, step number of passes 10.Therefore total reaction time is 20min.
(5) post processing: after anodized, is placed in deionized water by titanium sheet, ultrasonic cleaning 2min, then dries sample in an oven, baking temperature 65 DEG C, time 35min.
Adopt scanning electron microscopic observation implant surface pattern, there is a large amount of bowl configurations in titanium implant surface, bowl configurations major diameter is about 2-70 μm, and wide footpath is distributed in 2-38 μm of scope, and depth bounds is about 2-38 μm.
Embodiment 7
Other content as the content in embodiment 1, wherein:
Concentration of electrolyte in step (2): be raw material with potassium formate and ammonium acetate, it is 2mol/L that preparation contains formate ion concentration, and acetate ion concentration is the electrolyte of 1.5mol/L;
In step (3), setting bath temperature is 10 DEG C, and the distance of anode and negative electrode is 3cm;
Step (4) Anodic Oxidation process: adopt the pattern of progressively up-flow to carry out anodized after energising, first step current density value is set to 7mA/cm2, progressively raises, and often walks and all keeps 1min, up-flow value of going forward one by one is 4mA/cm2, step number of passes 5.
Adopt scanning electron microscopic observation implant surface pattern, there is a large amount of bowl configurations in titanium implant surface, bowl configurations major diameter is about 2-35 μm, and wide footpath is about 2-24 μm, and depth bounds is about 2-20 μm.
Embodiment 8
Other content as the content in embodiment 1, wherein:
Concentration of electrolyte in step (2): be raw material with sodium formate, potassium formate and ammonium acetate, it is 7mol/L that preparation contains formate ion concentration, and acetate ion concentration is the electrolyte of 2mol/L;
In step (3), setting bath temperature is 15 DEG C, and the distance of anode and negative electrode is 5cm;
Step (4) Anodic Oxidation process: adopt the pattern of progressively up-flow to carry out anodized after energising, first step current density value is set to 6mA/cm 2, progressively raise, often walk and all keep 7min, up-flow value of going forward one by one is 2.5mA/cm 2, step number of passes 15.
Adopt scanning electron microscopic observation implant surface pattern, there is a large amount of bowl configurations in titanium implant surface, bowl configurations major diameter is about 2-50 μm, and wide footpath is about 2-30 μm, and depth bounds is about 2-30 μm.
Embodiment 9
Other content as the content in embodiment 1, wherein:
Concentration of electrolyte in step (2): be raw material with sodium formate and ammonium acetate, it is 1mol/L that preparation contains formate ion concentration, and acetate ion concentration is the electrolyte of 1.8mol/L;
In step (3), setting bath temperature is 23 DEG C, and the distance of anode and negative electrode is 4cm;
Step (4) Anodic Oxidation process: adopt the pattern of progressively up-flow to carry out anodized after energising, first step current density value is set to 3.5mA/cm 2, progressively raise, often walk and all keep 9min, up-flow value of going forward one by one is 6mA/cm 2, step number of passes 12.
Adopt scanning electron microscopic observation implant surface pattern, there is a large amount of bowl configurations in titanium implant surface, bowl configurations major diameter is about 2-55 μm, and wide footpath is about 2-33 μm, and depth bounds is about 2-32 μm.
Test one
Carry out scanning electron microscopic observation to the titanium implant of embodiment 1, the formation of a large amount of micron bowl configurations of visible surface, the scanning electron microscopic picture of the implant surface after process is as Fig. 1.
Test two
Carry out sem test to the surface of titanium sheet sample prepared by embodiment 6, and adopt Nano-measuer, the micron bowl configurations of ImageJ software to sample does dimensional measurement and statistics.Major diameter minima is 16 μm, and maximum is 68 μm.Fig. 2 C is shown in the distribution of major diameter, can see and mainly be distributed in 20-44 μm of scope, account for 83%.The wide footpath minima recording larger bowl configurations is 10 μm, and maximum is 38.4 μm, and its scattergram is shown in Fig. 2 D, mainly 12-24 μm of distribution, and accounting 85%.The distribution density of larger pit is about 2.2/100 μm 2.ImageJ software is adopted to carry out automated border detection and areal calculation to bowl configurations larger in SEM figure, be that the area of the standard round of 10 μm is as marginal value using diameter, automatically the pit detected is as shown in Fig. 2 B fill area, and the maximum area detected is the area of a circle of 38.4 μm of diameters.Fig. 2 E is the area distribution plot of the larger pit automatically detected, is mainly distributed in the scope of the area of a circle being equivalent to 14-16 μm of diameter, accounts for 43.6%.
Test three
With sandblasted and acid-etching surface (SLA) and traditional anodized surface (S) for matched group, a series of biological assessment is carried out to class Bone resoiption pit surface (M) sample adopting embodiment 6 to prepare: the absorbability of bovine serum albumin, with the impact of sticking, breeding and break up of MG63 osteoblast Dual culture on cell.
Wherein, sandblasted and acid-etching surface (SLA): the white fused alumina blasting treatment by the pretreated titanium sheet sample of embodiment 6 by granularity being 60# in sandblasting machine, sample is about 3-5cm from jet opening distance, blasting pressure 0.4-0.6MPa, sandblasting tens of second, make each field color in the two sides of sample even, then successively after acetone, dehydrated alcohol, deionized water ultrasonic cleaning 10min, be placed in 18%HCl and 48%H 2sO 4acid etching 30min at 60 DEG C in isopyknic mix acid liquor, with deionized water rinsing, finally uses deionized water ultrasonic cleaning 15min, 50-70 DEG C of dry for standby in baking oven.
Traditional anodized surface (S): carry out anodized under 180V constant voltage mode by the pretreated titanium sheet sample of embodiment 6 in 1mol/L sodium acetate electrolyte, keep 1min after being raised to 180V.Then by sample ultrasonic cleaning 15min in deionized water, 50-70 DEG C of dry for standby in baking oven.
Result: as shown in Figure 3, compares with conventional anodization processed group with sandblasting acid etching group, and Novel bionic topographical surface significantly strengthens the absorption of bovine serum albumin, osteoblast adhesion, propagation and differentiation.In addition, alkaline phosphatase activities, collagen secretion and mineralization of extracellular matrix are also significantly improved in Novel bionic topographical surface group.

Claims (7)

1. one kind has the titanium implant of similar Bone resoiption pit body structure surface pattern, it is characterized in that: comprise titanium implant body and pit layer, the pit of described pit layer is for nibbling shape or cellular, and shape profile is tied similar with three-dimensional dimension to the osteoclast absorption lacuna that bone resorption is formed on surface of bone.
2. a kind of titanium implant with similar Bone resoiption pit body structure surface pattern according to claim 1, it is characterized in that: described pit major diameter is 2-80 μm, wide footpath is 2-40 μm, and the degree of depth is 2-40 μm.
3. a kind of titanium implant with similar Bone resoiption pit body structure surface pattern according to claim 1, is characterized in that:
Described titanium implant body is titanium implant or titanium sheet.
4. prepare a method for the titanium implant with similar Bone resoiption pit body structure surface pattern, it is characterized in that:
Comprise the following steps:
(1) pretreatment: by titanium implant cleaning treatment, stand-by after dry in baking oven, baking temperature 50-70 DEG C, time 20-60min;
(2) electrolyte quota: preparation formates/acetate mixed electrolytic solution, the molar concentration of formate ion is 0.05 ~ 10mol/L, and the molar concentration of acetate ion is 0 ~ 2.4mol/L;
(3) anodic oxidation device: take adjustable D. C regulated as anodic oxidation power supply, titanium implant in step (1) is connected as anode with positive source, face of cylinder hollow cathode is made with titanium foil or stainless steel foil, be connected with power cathode as negative electrode around titanium implant, again by pending for titanium implant partially submerged enter under liquid level, electrolyte in step (2) is placed in electrolysis bath, magnetic agitation;
(4) anodized: after energising, initial current density values is set to 2.5-10mA/cm2, progressively raise, often walking the retention time is 1-10min, and up-flow goes forward one by one value for 2.5-10mA/cm2, each process is fixed up-flow and is gone forward one by one value and retention time, step number of passes 5-20;
(5) post processing: the titanium implant in ultrasonic cleaning step again (4), dry, baking temperature is 50-70 DEG C, and time 20-60min, to obtain final product.
5. a kind of preparation method with the titanium implant of similar Bone resoiption pit body structure surface pattern according to claim 4, it is characterized in that: formates described in step (2) be sodium formate, potassium formate or ammonium formate one or more, acetate be sodium acetate, potassium acetate or ammonium acetate one or more.
6. a kind of preparation method with the titanium implant of similar Bone resoiption pit body structure surface pattern according to claim 4, is characterized in that: described in step (3), the distance of anode and negative electrode is 3-5cm.
7. a kind of preparation method with the titanium implant of similar Bone resoiption pit body structure surface pattern according to claim 4, is characterized in that: controlling electrolyte temperature in step (3) is 10 DEG C-30 DEG C.
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CN108486633A (en) * 2018-06-29 2018-09-04 四川大学 It is a kind of that there is hydrophobic and superhydrophobic characteristic titanium or titanium alloy surface and preparation method
CN110699733A (en) * 2019-11-20 2020-01-17 中国计量大学 Preparation method, product and application of titanium alloy porous oxide film
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CN114346441B (en) * 2022-01-21 2024-06-04 中国人民解放军总医院第一医学中心 Dental implant surface treatment method

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CN108486633A (en) * 2018-06-29 2018-09-04 四川大学 It is a kind of that there is hydrophobic and superhydrophobic characteristic titanium or titanium alloy surface and preparation method
CN110699733A (en) * 2019-11-20 2020-01-17 中国计量大学 Preparation method, product and application of titanium alloy porous oxide film
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