CN105496577B - Titanium implant and preparation method with similar Bone resoiption pit surface topography - Google Patents
Titanium implant and preparation method with similar Bone resoiption pit surface topography Download PDFInfo
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- CN105496577B CN105496577B CN201510915424.5A CN201510915424A CN105496577B CN 105496577 B CN105496577 B CN 105496577B CN 201510915424 A CN201510915424 A CN 201510915424A CN 105496577 B CN105496577 B CN 105496577B
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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
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- 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
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- 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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Abstract
The invention discloses a kind of titanium implants and preparation method thereof with similar Bone resoiption pit body structure surface pattern.Use formates/acetic acid mixed salt solution for electrolyte, the concentration of formate ion is in 0.05 ~ 10 mol/L ranges, and the concentration of acetate ion is in 0 ~ 2.4 mol/L ranges.Anodized is carried out to titanium implant using staged flow mode, initial current density values are set as 2.5 10mA/cm after energization2, it is stepped up, it is 1 10 min often to walk the retention time, and it is 2.5 10mA/cm to flow up progressive value2, it is per treatment it is fixed flow up progressive value and retention time, walk number of passes 5 20, current-time curvel is in uplink step.The inventive method can prepare shape contour in titanium implant surface and three-dimensional dimension is similar to the micron bowl configurations of Bone resoiption pit.Cell biology evaluation result shows that the titanium implant with similar Bone resoiption pit body structure surface pattern prepared by the present invention can remarkably promote function of osteoblast.
Description
Technical field
The invention belongs to oral cavity titanium implant surface processing technology fields, are related to a kind of with imitative Bone resoiption pit structure table
The titanium implant and preparation method of face pattern.
Background technology
Tooth-planting treatment has become the treatment means that clinical oral Anodontia repair is best now.The surface of planting body
Property is to influence one of most important factor of its osseointegration character, and therefore, the process for treating surface of planting body is also to influence plantation
The key element of body product quality.Although the implant system clinically used at present uses a variety of implant surface processing
Technology can meet the requirement of general planting treatment.But encounter the bad feelings of certain patients itself alveolar bone sclerotin bone amount
The emerging therapeutic modality such as condition or immediate implant Immediate prosthesis just proposes higher want to the Integrated implant ability of planting body
It asks.Therefore, the novel surface treatment technology for the Integrated implant speed and intensity that further research and development can improve planting body becomes plantation
One of the focus on research direction in body field.
The process for treating surface of planting body has many methods, physics, chemical, biological etc., pass through these sides
Method can bring the change of implant surface pattern, surface chemical composition and surface energy.Wherein, surface topography is important
One of factor.Different surface treatment methods can obtain the surface topography of great disparity, and such as groove is rough irregular
Surface texture, micropore or bowl configurations, nano particle or nano tube structure etc. [David M, Ehrenfest D, Coelho PG,
Kang BS,Sul YT,Albrektsson T.Classification of osseointegrated implant
surfaces:materials.chemistry and topography.Trends in Biotechnology,2010,28
(4):198~206].It is most advantageous which type of surface topography forms Integrated implant to planting body
In recent years, academia proposes bionic theory.Studies have shown that the forming process at planting body-synosteosis interface
It is similar to naturally new and old synosteosis interface.In natural bon e formation or reconstruction process, osteoclast is made in old bone surface bone information
Play an important roll to the formation at new and old synosteosis interface with absorption lacuna structure is formed by.Therefore, J.E.Davies etc. recognizes
There should be the topological surface topography of similar Bone resoiption pit structure for optimal planting body.Bone resoiption pit, it is also referred to as bold and unconstrained
Not this lacuna (Howship ' s lacunae) summarizes document to Bone resoiption pit in cellular or nibble the lacuna spline structure of shape
Description, characterize data, absorption lacuna have following shape characteristic：1. the profile and edge clear of absorption lacuna are distinguishable, and not
It is clear to absorb the boundary of bone face, as the pit of downward on level land " excavating ".2. the pattern of single absorption lacuna in subcircular or
Oval, multiple absorption lacunas are got together, and channel form are also presented, but the contour line of absorption lacuna is smooth.Size characteristic：It inhales
The length and width diameter for receiving lacuna is distributed in several microns to dozens or even hundreds of micron, and depth is micro- to tens up to several microns
Rice.It can be seen that Bone resoiption pit has distinct shape characteristic.
There are some technical methods that can prepare pit shape structure in titanium implant surface both at home and abroad, common method is spray
Sand processing.The SLA surface implants of Straumann house journals are prepared by the method for sandblasting acid etching in implant surface
For diameter in 30~100 μm of micron bowl configurations and 1~3 μm of etch pit structure, the principle of sandblasting is will be white under certain air pressure
Corundum, titanium oxide, SiC particulate, diamond dust are ejected into implant surface, and pit shape structure is formed under the shock of sand grains.Sand grains
Grain size is bigger, and air pressure is bigger, and the diameter and depth of pit are bigger.The principle of acid etching is to utilize the acid solutions such as sulfuric acid, hydrochloric acid, hydrofluoric acid
Corrosiveness, react with titanium, titanium made to dissolve, due to surface different zones be dissolved degree it is different, to be formed
Pit shape structure, acid etching can be combined with sandblasting, can also individually implement.Sandblasting：Blur margin is clear, and depth is inadequate.
The Chinese patent CN200510062209.1 that can be obtained discloses one kind, and " being prepared on pure-titanium tooth implantation surface has
The method of bioactivity, porous structure " constructs a diameter of 10~30 μ using the method for sandblasting under Buddha's warrior attendant sand blasting 4bar pressure
The micron order pit of m.The bowl configurations of formation are dimensionally in the size range of Bone resoiption pit, but there are bright for shape
Significant difference is different, shape be it is irregular, it is related with the irregular shape of grit blast.
Chinese patent CN201210052274.6 discloses one kind and " it is double preparing micron-submicron in titanium alloy dental implant surface
The method of grade micro-structure ", in group as HCl 88-110g/L, HF 39-63g/L, NH4It is used in the electrolyte of F 10-25g/L
The method of electrolytic etching handles titanium implant, and the micron order micro-structure surface of 2-5 μm of diameter is prepared.But this method
The micron bowl configurations size of preparation is less than normal compared with absorption lacuna.Zhao etc. is using electrochemistry micro Process method in titanium surface construction
Regularly arranged micron bowl configurations with controlled dimensions (10,30,100 μm), but this method is appropriate only for outside preparation
The smooth titanium sheet of shape rule, is not suitable for the titanium implant product of shape of threads.
It is multiple that Chinese patent CN201210232397.8 discloses a kind of micrometer/nanometer multistage formed on the titanium-based bottom surface
The method for closing the anatase titanium dioxide film layer of pore structure.Acid etch processing, warp are carried out using sulfuric acid and hydrochloric acid mixed solution
Micrometer grade hole structure is formed in the titanium-based bottom surface after peracid etching processing, then carries out anodized, electrolyte is
0.3wt%NH4F+0.2wt%H2O2Ethylene glycol solution nano grade pore structure is formed in structure in the micron-scale, that is, formed micron/
Nanometer hierarchical composite pore structural；It is heat-treated, forming micrometer/nanometer multistage in titanium substrate material surface after Overheating Treatment answers
Close the anatase titanium dioxide film layer of pore structure.The aperture of micron openings is 2-6 μm, and the aperture of nano-pore is 10-100nm.Phase
It is obviously more much smaller than Bone resoiption pit micron openings aperture.In conclusion existing patented technology method cannot be in titanium both at home and abroad
Implant surface prepares similar Bone resoiption pit porous structure.
Invention content
In order to solve the above technical problems, the present invention provides a kind of titaniums with imitative Bone resoiption pit body structure surface pattern
Planting body and preparation method thereof.
Solve a kind of titanium kind with similar Bone resoiption pit body structure surface pattern in the present invention of the above technical problem
Implant, it is characterised in that：Including titanium implant ontology and pit layer, the pit of the pit layer is to nibble shape or cellular, shape
Shape profile and three-dimensional dimension are similar to the osteoclast absorption lacuna knot that bone resorption is formed on bone face, and similarity can be
96-100%.
The pit major diameter is 2-80 μm, and wide diameter is 2-40 μm, and depth is 2-40 μm.
The titanium implant ontology is titanium implant or titanium sheet.
A kind of method preparing the titanium implant with similar Bone resoiption pit body structure surface pattern, feature in the present invention
It is：
Include the following steps:
(1) it pre-processes：It is for use after dry in baking oven by titanium implant cleaning treatment, 50-70 DEG C of drying temperature, time 20-
60min；To remove the greasy dirt and impurity of titanium implant surface.
(2) electrolyte quota：Formates/acetate mixed electrolytic solution is prepared, the molar concentration of formate ion is 0.05
The molar concentration of~10mol/L, acetate ion are 0~2.4mol/L；
The formation of the porous structure for the oxidation film that the type and dosage of electrolyte form surface of metal titanium and character tool
Have a great impact, formate ion and acetate ion have special field-enhanced dissolution effect to titanium oxide, are to form pit
The main reason for shape structure and necessary condition, the composition and concentration of anodic oxidation electrolyte determine obtained anode oxide film
The shape feature of porous structure can not using the electrolyte prescription without both ions under the conditions of same electrical parameter
Obtain the bowl configurations of the analogous shape, size that are prepared in the present invention.
(3) anodic oxidation device：Using adjustable D. C regulated as anodic oxidation power supply, the titanium in step (1) is planted
Body is connected as anode with positive pole, and cylindrical surface hollow cathode is made with titanium foil or stainless steel foil, around titanium implant conduct
Cathode is connected with power cathode, then by titanium implant it is pending it is partially submerged enter liquid level under, electrolyte in step (2) is placed in electricity
It solves in slot, magnetic agitation；Electrolytic cell can be glass or organic glass electrolytic cell.
The effect of cylindrical cathode is keep each zone current Density Distribution of planting body substantially uniform, magnetic agitation
Effect is that electrolyte in reaction process is made to stir evenly.
(4) anodized：Initial current density values are set as 2.5-10mA/cm2 after energization, are stepped up, and often step is protected
It is 1-10min to hold the time, and it is 2.5-10mA/cm2 to flow up progressive value, and fixation per treatment flows up progressive value and retention time, step
Number of passes 5-20, current-time curvel are in uplink step；
Anodized gradually flow mode after energization：Staged flow mode can be used, when often step keeps certain
Between, current-time curvel is in uplink step.
The effect of staged flow mode is to provide suitable electric field power and must for the field-enhanced dissolution effect of acid ion
The dissolution time wanted.
(5) it post-processes：The titanium implant being cleaned by ultrasonic in deionized water again in step (4), dry, drying temperature is
50-70 DEG C, time 20-60min to get to titanium implant there is the surface topography of similar Bone resoiption pit structure.
The effect of ultrasonic cleaning is the precipitation or impurity substances that elution remains in titanium implant surface, reaches cleaning planting body
The effect on surface.
Formates described in step (2) is that sodium formate, potassium formate or ammonium formate are one or more kinds of, and acetate is acetic acid
Sodium, potassium acetate or ammonium acetate are one or more kinds of.
Electrolyte prescription is mainly neutral salt solution, non-volatile, can long-term preservation, stablize, it is nontoxic, it is environmentally friendly, at
This is cheap, is conducive to realize industrial production.When configuring high concentration electrolyte, the reagent that needs Selective dissolution degree sufficiently large.
Anode described in step (3) is 3-5cm at a distance from cathode.
The control electrolyte temperature is 10 DEG C -30 DEG C in step (3), and temperature is to field-enhanced dissolution speed and oxide layer
It forms speed to have an impact, when temperature is too low or excessively high, implementation result can not be obtained.
Titanium implant is after preparation in the present invention, the visible a large amount of bowl configurations of implant surface, in nibbling shape or cell
Shape, edge clear are demarcated clear with flat site, shape contour and three-dimensional dimension with osteoclast on bone face bone information
It is similar to act on the absorption lacuna structure formed.
What any description above method was prepared there is the titanium implant of imitative Bone resoiption pit body structure surface pattern to belong to
In protection scope of the present invention.All features disclosed in this specification or disclosed all methods or in the process the step of, remove
Other than mutually exclusive feature and/or step, it can combine in any way.
Any feature disclosed in this specification (including any accessory claim, abstract), unless specifically stated,
It is replaced by other equivalent or with similar purpose alternative features.That is, unless specifically stated, each feature is a series of
An example in equivalent or similar characteristics.
Description of the drawings
Figure 1A-Fig. 1 D are titanium implant scanning electron microscopic observation figure in embodiment 1 in the present invention
Wherein A is titanium implant millimeter figure；B is 500 μm of figures of titanium implant；C is 50 μm of figures of titanium implant；D plants for titanium
20 μm of figures of body
Fig. 2A -2E are the micron concave state quantitative analysis figure on class Bone resoiption pit surface in the present invention
Wherein A is micron pit SEM figures；B is that micron pit profile detects figure automatically；C is micron pit major diameter statistical chart；
D is the wide diameter statistical chart of micron pit；E is micron pit area statistical chart
Class Bone resoiption pit topographical surface (M) and sandblasting acid etching (SLA) and conventional anodization in Fig. 3 A-3F present invention
(S) biological evaluation result of surface sample
Specific implementation mode
Embodiment below facilitates a better understanding of the present invention, but does not limit the present invention.Experiment in following embodiments
Method is unless otherwise specified conventional method.Titanium transplanting body ontology and test material as used in the following examples, such as nothing
Specified otherwise is to be commercially available from conventional biochemical reagent supplier.
A kind of titanium implant with similar Bone resoiption pit body structure surface pattern in the present invention, including titanium implant sheet
Body and pit layer, the pit of the pit layer are to nibble shape or cellular, shape contour and three-dimensional dimension with osteoclast in bone
The absorption lacuna knot that bone resorption is formed on face is similar, and similarity can be 96-100%.Pit major diameter is 2-80 μm, and wide diameter is
2-40 μm, depth is 2-40 μm, and titanium implant ontology is titanium implant or titanium sheet.
Below in conjunction with specific example, the process invented further is elaborated, specific embodiment is as follows：
Embodiment 1：
(1) it pre-processes：By mechanical processing or the titanium implant acetone of 3D printing manufacture, absolute ethyl alcohol, deionization moisture
It is not cleaned by ultrasonic 5min, washes away the greasy dirt and impurity on surface；It dries in an oven again, 50 DEG C of drying temperature, time 30min.
(2) electrolyte：It is electrolyte with sodium formate and sodium acetate trihydrate, prepares a concentration of 0.7mol/ containing formate ion
L, the electrolyte of a concentration of 0.3mol/L of acetate ion.
(3) anodic oxidation device：With D.C. regulated power supply WYJ-300V3A (Shanghai all one's effort Electrical Appliances Co., Ltd) for anode
Power supply is aoxidized, pretreated titanium implant is connected as anode with positive pole, the titanium foil of 500 × 80 × 0.1mm is curved
Cylindric circular titanium implant is connected as cathode with power cathode, and anode is 3cm at a distance from cathode, and planting body is pending
It is partially submerged enter liquid level under, the electrolyte of preparation is placed in 500mL glass beakers, beaker is placed in heat-collecting magnetic stirring device
In, bath temperature is set as 25 DEG C.
(4) anodized：Anodized is carried out using the pattern gradually flowed up after energization, first step electric current is close
Angle value is set as 5mA/cm2, it is stepped up, often walks and keep 2min, it is 5mA/cm to flow up progressive value2, number of passes 10 is walked, thus it is total
Reaction time is 20min.
(5) it post-processes：After anodized, titanium implant is placed in deionized water, is cleaned by ultrasonic 2min, then
Sample, 70 DEG C of drying temperature, time 60min are dried in an oven.
Using scanning electron microscopic observation implant surface pattern, there are a large amount of bowl configurations, bowl configurations in titanium implant surface
Major diameter is about 2-68 μm, and about 2-38.4 μm of wide diameter, depth bounds are about 2-38 μm.
Embodiment 2
(1) it pre-processes：By mechanical processing or the titanium implant petroleum ether of 3D printing manufacture, absolute ethyl alcohol, deionized water
It is cleaned by ultrasonic 5min respectively, washes away the greasy dirt and impurity on surface；It dries in an oven again, 70 DEG C of drying temperature, time 20min.
(2) electrolyte：It is raw material with ammonium formate and potassium acetate, prepares a concentration of 0.7mol/L containing formate ion, acetic acid
Ion concentration is the electrolyte of 0.5mol/L.
(3) anodic oxidation device：With D.C. regulated power supply WYJ-300V1A (Shanghai all one's effort Electrical Appliances Co., Ltd) for anode
Power supply is aoxidized, pretreated titanium implant is connected as anode with positive pole, the titanium foil of 500 × 80 × 0.1mm is curved
Cylindric circular titanium implant is connected as cathode with power cathode, and anode is 4cm at a distance from cathode, and planting body is pending
It is partially submerged enter liquid level under, the electrolyte of preparation is placed in glass beaker, beaker is placed in cryogenic thermostat bath, set water
Bath temperature is 20 DEG C.
(4) anodized：Anodized is carried out using the pattern gradually flowed up after energization, first step electric current is close
Angle value is set as 2.5mA/cm2, it is stepped up, often walks and keep 5min, it is 5mA/cm to flow up progressive value2, walk number of passes 10.Therefore
Total reaction time is 50min.
(5) it post-processes：After anodized, titanium implant is placed in deionized water, is cleaned by ultrasonic 3min, then
Sample, 50 DEG C of drying temperature, time 30min are dried in an oven.
Using scanning electron microscopic observation implant surface pattern, there are a large amount of bowl configurations, bowl configurations in titanium implant surface
Major diameter is about 2-40 μm, and wide diameter is distributed in 2-24 μ ms, and depth bounds are about 2-26 μm.
Embodiment 3
(1) it pre-processes：Titanium implant acetone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 5min respectively, wash away surface
Greasy dirt and impurity；It dries in an oven again, 60 DEG C of drying temperature, time 30min.
(2) electrolyte：It is raw material with sodium formate and sodium acetate, prepares a concentration of 10mol/L containing formate ion, acetate
Ion concentration is the electrolyte of 2.4mol/L.
(3) anodic oxidation device：With D.C. regulated power supply WYJ-200V1A (Shanghai all one's effort Electrical Appliances Co., Ltd) for anode
Power supply is aoxidized, pretreated titanium implant is connected as anode with positive pole, the titanium foil of 500 × 80 × 0.1mm is curved
Cylindric circular titanium implant is connected as cathode with power cathode, and anode is 5cm at a distance from cathode, and planting body is pending
It is partially submerged enter liquid level under, the electrolyte of preparation is placed in 500mL glass beakers, beaker is placed in heat-collecting magnetic stirring device
In, bath temperature is set as 25 DEG C.
(4) anodized：Anodized is carried out using the pattern gradually flowed up after energization, first step electric current is close
Angle value is set as 10mA/cm2, it is stepped up, often walks and keep 2min, it is 5mA/cm to flow up progressive value2, walk number of passes 10.Therefore it is total
Reaction time is 20min.
(5) it post-processes：After anodized, titanium implant is placed in deionized water, is cleaned by ultrasonic 4min, then
Sample, 60 DEG C of times of drying temperature, time 40min are dried in an oven.
Using scanning electron microscopic observation implant surface pattern, there are a large amount of bowl configurations, bowl configurations in titanium implant surface
Major diameter is about 2-50 μm, and wide diameter is distributed in 2-30 μ ms, and depth bounds are about 2-30 μm.
Embodiment 4
(1) it pre-processes：Titanium implant acetone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 5min respectively, wash away surface
Greasy dirt and impurity；It dries in an oven again, 65 DEG C of drying temperature, time 25min.
(2) electrolyte：It is raw material with sodium formate, prepares the electrolyte of a concentration of 0.05mol/L containing formate ion.
(3) anodic oxidation device：With D.C. regulated power supply WYJ-300V3A (Shanghai all one's effort Electrical Appliances Co., Ltd) for anode
Power supply is aoxidized, pretreated titanium implant is connected as anode with positive pole, the titanium foil of 500 × 80 × 0.1mm is curved
Cylindric circular titanium implant is connected as cathode with power cathode, and anode is 3.5cm at a distance from cathode, and planting body is waited locating
Manage it is partially submerged enter liquid level under, the electrolyte of preparation is placed in 500mL glass beakers, beaker is placed in heat-collecting magnetic stirring
In device, bath temperature is set as 25 DEG C.
(4) anodized：Anodized is carried out using the pattern gradually flowed up after energization, first step electric current is close
Angle value is set as 5mA/cm2, it is stepped up, often walks and keep 10min, it is 5mA/cm to flow up progressive value2, walk number of passes 20.Therefore it is total
Reaction time is 200min.
(5) it post-processes：After anodized, titanium implant is placed in deionized water, is cleaned by ultrasonic 2min, then
Sample, 55 DEG C of drying temperature, time 60min are dried in an oven.
Using scanning electron microscopic observation implant surface pattern, there are a large amount of bowl configurations, bowl configurations in titanium implant surface
Major diameter is about 2-25 μm, and wide diameter is distributed in 2-15 μ ms, and depth bounds are about 2-15 μm.
Embodiment 5
(1) it pre-processes：Titanium implant acetone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 5min respectively, wash away surface
Greasy dirt and impurity；It dries in an oven again, 55 DEG C of drying temperature, time 30min.
(2) electrolyte：It is raw material with sodium formate and sodium acetate, prepares a concentration of 5mol/L containing formate ion, acetate
Ion concentration is the electrolyte of 1mol/L.
(3) anodic oxidation device：With D.C. regulated power supply WYJ-200V1A (Shanghai all one's effort Electrical Appliances Co., Ltd) for anode
Power supply is aoxidized, pretreated titanium implant is connected as anode with positive pole, the titanium foil of 500 × 80 × 0.1mm is curved
Cylindric circular titanium implant is connected as cathode with power cathode, and anode is 4cm at a distance from cathode, and planting body is pending
It is partially submerged enter liquid level under, the electrolyte of preparation is placed in 500mL glass beakers, beaker is placed in heat-collecting magnetic stirring device
In, bath temperature is set as 30 DEG C.
(4) anodized：Anodized is carried out using the pattern gradually flowed up after energization, first step electric current is close
Angle value is set as 5mA/cm2, is stepped up, and often walks and keeps 2min, and it is 5mA/cm2 to flow up progressive value, walks number of passes 10.Therefore it is total
Reaction time is 20min.
(5) it post-processes：After anodized, titanium implant is placed in deionized water, is cleaned by ultrasonic 4min, then
Sample, 65 DEG C of drying temperature, time 30min are dried in an oven.
Using scanning electron microscopic observation implant surface pattern, there are a large amount of bowl configurations, bowl configurations in titanium implant surface
Major diameter is about 2-80 μm, and wide diameter is distributed in 2-40 μ ms, and depth bounds are about 2-35 μm.
Embodiment 6
(1) it pre-processes：The pure titanium sheet of the trade mark TA1 of diameter 15mm, thickness 1mm use acetone, anhydrous second after sanding and polishing
Alcohol, deionized water are cleaned by ultrasonic 5min respectively, wash away the greasy dirt and impurity on surface；It dries in an oven again, 70 DEG C of drying temperature,
Time 25min.
(2) electrolyte：It is raw material with sodium formate and sodium acetate, prepares a concentration of 0.7mol/L containing formate ion, acetic acid
Ion concentration is the electrolyte of 0.3mol/L.
(3) anodic oxidation device：With D.C. regulated power supply WYJ-200V1A (Shanghai all one's effort Electrical Appliances Co., Ltd) for anode
Power supply is aoxidized, pretreated titanium sheet is connected as anode with positive pole, the titanium foil of 500 × 80 × 0.1mm is curved into cylinder
Shape is connected as cathode with power cathode around titanium implant, and anode is 4cm at a distance from cathode, and titanium sheet is submerged into liquid level
Under, the electrolyte of preparation is placed in 500mL glass beakers, beaker is placed in heat-collecting magnetic stirring device, sets water-bath temperature
Degree is 20 DEG C.
(4) anodized：Anodized is carried out using the pattern gradually flowed up after energization, first step electric current is close
Angle value is set as 5mA/cm2, is stepped up, and often walks and keeps 2min, and it is 5mA/cm2 to flow up progressive value, walks number of passes 10.Therefore it is total
Reaction time is 20min.
(5) it post-processes：After anodized, titanium sheet is placed in deionized water, is cleaned by ultrasonic 2min, then drying
Sample, 65 DEG C of drying temperature, time 35min are dried in case.
Using scanning electron microscopic observation implant surface pattern, there are a large amount of bowl configurations, bowl configurations in titanium implant surface
Major diameter is about 2-70 μm, and wide diameter is distributed in 2-38 μ ms, and depth bounds are about 2-38 μm.
Embodiment 7
Content in other contents such as embodiment 1, wherein：
Concentration of electrolyte in step (2)：It is raw material with potassium formate and ammonium acetate, prepares a concentration of containing formate ion
2mol/L, the electrolyte of a concentration of 1.5mol/L of acetate ion；
Bath temperature is set in step (3) as 10 DEG C, anode is 3cm at a distance from cathode；
The processing of step (4) Anodic Oxidation：Anodized, the first step are carried out using the pattern gradually flowed up after energization
Current density value is set as 7mA/cm2, is stepped up, and often walks and keeps 1min, and it is 4mA/cm2 to flow up progressive value, walks number of passes 5
It is a.
Using scanning electron microscopic observation implant surface pattern, there are a large amount of bowl configurations, bowl configurations in titanium implant surface
Major diameter is about 2-35 μm, and about 2-24 μm of wide diameter, depth bounds are about 2-20 μm.
Embodiment 8
Content in other contents such as embodiment 1, wherein：
Concentration of electrolyte in step (2)：It is raw material with sodium formate, potassium formate and ammonium acetate, prepares dense containing formate ion
Degree is 7mol/L, the electrolyte of a concentration of 2mol/L of acetate ion；
Bath temperature is set in step (3) as 15 DEG C, anode is 5cm at a distance from cathode；
The processing of step (4) Anodic Oxidation：Anodized, the first step are carried out using the pattern gradually flowed up after energization
Current density value is set as 6mA/cm2, it is stepped up, often walks and keep 7min, it is 2.5mA/cm to flow up progressive value2, walk number of passes 15
It is a.
Using scanning electron microscopic observation implant surface pattern, there are a large amount of bowl configurations, bowl configurations in titanium implant surface
Major diameter is about 2-50 μm, and about 2-30 μm of wide diameter, depth bounds are about 2-30 μm.
Embodiment 9
Content in other contents such as embodiment 1, wherein：
Concentration of electrolyte in step (2)：It is raw material with sodium formate and ammonium acetate, prepares a concentration of containing formate ion
1mol/L, the electrolyte of a concentration of 1.8mol/L of acetate ion；
Bath temperature is set in step (3) as 23 DEG C, anode is 4cm at a distance from cathode；
The processing of step (4) Anodic Oxidation：Anodized, the first step are carried out using the pattern gradually flowed up after energization
Current density value is set as 3.5mA/cm2, it is stepped up, often walks and keep 9min, it is 6mA/cm to flow up progressive value2, walk number of passes 12
It is a.
Using scanning electron microscopic observation implant surface pattern, there are a large amount of bowl configurations, bowl configurations in titanium implant surface
Major diameter is about 2-55 μm, and about 2-33 μm of wide diameter, depth bounds are about 2-32 μm.
Experiment one
Electronic Speculum observation is scanned to the titanium implant of embodiment 1, it is seen that the formation of a large amount of micron bowl configurations in surface, place
The scanning electron microscopic picture of implant surface after reason such as Figure 1A-Fig. 1 D.
Experiment two
Electronic Speculum test is scanned to the surface of the titanium sheet sample of the preparation of embodiment 6, and uses Nano-measuer,
Image J softwares do dimensional measurement and statistics to the micron bowl configurations of sample.Major diameter minimum value is 16 μm, and maximum value is 68 μ
m.Fig. 2 C are shown in the distribution of major diameter, it can be seen that are mainly distributed on 20-44 μ ms, account for 83%.Measure the width of larger bowl configurations
Diameter minimum value is 10 μm, and maximum value is 38.4 μm, and distribution map is shown in Fig. 2 D, mainly in 12-24 μm of distribution, accounting 85%.
The distribution density of larger pit is about 2.2/100 μm2.Larger bowl configurations in SEM figures are carried out certainly using Image J softwares
Dynamic edge detection and areal calculation, using the area of a diameter of 10 μm of standard round as critical value, the pit automatically detected is such as
Shown in Fig. 2 B filling regions, the maximum area detected is the area of a circle of 38.4 μ m diameters.Fig. 2 E be automatically detect it is larger
The area distribution plot of pit is mainly distributed on the range for the area of a circle for being equivalent to 14-16 μ m diameters, accounts for about 43.6%.
Experiment three
With sandblasted and acid-etching surface (SLA) and traditional anodized surface (S) for control group, to using implementation
Class Bone resoiption pit surface (M) sample prepared by example 6 has carried out a series of biological assessments:The adsorption energy of bovine serum albumin(BSA)
Power co-cultures the influence sticked, be proliferated and broken up to cell with MG63 osteoblasts.
Wherein, sandblasted and acid-etching surface (SLA)：Granularity is used in sand-blasting machine by 6 pretreated titanium sheet sample of embodiment
For the white fused alumina blasting treatment of 60#, sample sandblasting tens of seconds, makes from jet opening distance about 3-5cm, blasting pressure 0.4-0.6MPa
Each field color in two sides of sample is uniform, after then acetone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 10min successively, is placed in
18%HCl and 48%H2SO4Acid etching 30min at 60 DEG C, is rinsed with deionized water, is finally used in isometric mix acid liquor
Deionized water is cleaned by ultrasonic 15min, is dried for standby for 50-70 DEG C in baking oven.
Traditional anodized surface (S)：It is electrolysed in 1mol/L sodium acetates by 6 pretreated titanium sheet sample of embodiment
Anodized is carried out in liquid under 180V constant voltage modes, 1min is kept after being raised to 180V.Then in deionized water by sample
It is cleaned by ultrasonic 15min, is dried for standby for 50-70 DEG C in baking oven.
As a result：As shown in figure 3, compared with sandblasting acid etching group and conventional anodization processing group, novel bionic topographical surface
Significantly increase absorption, osteoblast adhesion, proliferation and the differentiation of bovine serum albumin(BSA).In addition, alkaline phosphatase activities, collagen point
It secretes and is also significantly improved in novel bionic topographical surface group with mineralization of extracellular matrix.
Claims (4)
1. a kind of preparation method with the titanium implant similar to Bone resoiption pit body structure surface pattern, it is characterised in that：It is described
Titanium implant includes titanium implant ontology and pit layer, and the pit of the pit layer is to nibble shape or cellular, shape contour and
Three-dimensional dimension is similar to the absorption lacuna knot that osteoclast is formed on bone face by bone resorption, and the pit major diameter is 2-80
μm, wide diameter is 2-40 μm, and depth is 2-40 μm, and the titanium implant ontology is titanium implant piece or titanium sheet；
The preparation method comprises the following steps:
(1) it pre-processes：It is for use after dry in baking oven by titanium implant cleaning treatment, 50-70 DEG C of drying temperature, time 20-
60min；
(2) electrolyte quota：Formates/acetate mixed electrolytic solution is prepared, the molar concentration of formate ion is 0.05 ~ 10
The molar concentration of mol/L, acetate ion are 0 ~ 2.4 mol/L；
(3) anodic oxidation device：Using adjustable D. C regulated as anodic oxidation power supply, by step（1）In titanium implant make
It is connected with positive pole for anode, cylindrical surface hollow cathode is made with titanium foil or stainless steel foil, around titanium implant as cathode
Be connected with power cathode, then by titanium implant it is pending it is partially submerged enter liquid level under, by step（2）Middle electrolyte is placed in electrolytic cell
In, magnetic agitation；
(4) anodized：Initial current density values are set as 2.5-10mA/cm after energization2, it is stepped up, when often step is kept
Between be 1-10 min, flow up it is progressive value be 2.5-10mA/cm2, it is per treatment it is fixed flow up progressive value and retention time, walk number of passes
5-20；
(5) it post-processes：It is cleaned by ultrasonic step again（4）In titanium implant, dry, drying temperature is 50-70 DEG C, time 20-
60min to get.
2. a kind of preparation side with the titanium implant similar to Bone resoiption pit body structure surface pattern according to claim 1
Method, it is characterised in that：Step（2）Described in formates be that sodium formate, potassium formate or ammonium formate are one or more kinds of, acetate
It is one or more kinds of for sodium acetate, potassium acetate or ammonium acetate.
3. a kind of preparation side with the titanium implant similar to Bone resoiption pit body structure surface pattern according to claim 1
Method, it is characterised in that：Step（3）Described in anode at a distance from cathode be 3-5cm.
4. a kind of preparation side with the titanium implant similar to Bone resoiption pit body structure surface pattern according to claim 1
Method, it is characterised in that：Step（3）Middle control electrolyte temperature is 10 DEG C -30 DEG C.
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