CN109731135A

CN109731135A - A kind of hydrophilic treatment process of implant surface

Info

Publication number: CN109731135A
Application number: CN201910177923.7A
Authority: CN
Inventors: 钱晓锦; 曹云鹏; 徐骏伟
Original assignee: JIANGSU TRAUSIM MEDICAL INSTRUMENT CO Ltd
Current assignee: JIANGSU TRAUSIM MEDICAL INSTRUMENT CO Ltd
Priority date: 2019-03-07
Filing date: 2019-03-07
Publication date: 2019-05-10
Anticipated expiration: 2039-03-07
Also published as: CN109731135B

Abstract

The invention belongs to planting body technical fields, and in particular to one kind can be improved the hydrophilic treatment process of implant surface.Include: that planting body is first subjected to sandblasting and acid etching, then carry out alkali heat-treatment and plasma oxidation processing, make the more uniform densification of second level pit of implant surface, finally treated that planting body is directly immersed in adjusts the MgCl of pH value by plasma oxidation₂、CaCl₂It is impregnated with the mixed solution of NaCl, carries out hydrophilic treated to get preferable hydrophilic planting body is arrived.Implant surface prepared by the present invention can not only improve the mechanical interlock of planting body and bone tissue, promote the suction-operated of bioactive molecule and cell, be conducive to the adherency proliferation of cell, its surface energy and wetability are also improved simultaneously, the initial stage synosteosis speed for accelerating planting body, realizes quick Integrated implant；Simple process is suitble to commercially produce.

Description

A kind of hydrophilic treatment process of implant surface

Technical field

The invention belongs to planting body technical fields, and in particular to one kind can be improved the hydrophilic processing work of implant surface Skill.

Background technique

Titanium alloy material is repaired field in organ defect and is applied because of its excellent biocompatibility and excellent mechanical performance More and more extensive, the titanium-based biomaterial based on pure titanium or titanium alloy becomes the preferred material of current mouth cavity planting body.But from Clinical demand angle, however it remains need to improve the bioactivity of material, improve efficiency and effect of the material in conjunction with bone tissue The problems such as.The factor for influencing Integrated implant mainly has the material and shape of planting body, surface topography, chemical characteristic, loading condition, outer Shell operation and the individual difference of patient etc..For the initiative for improving implant osseointegration, planting body is promoted to be formed with surrounding tissue Good bony union, copes with its surface topography and chemical component improves, so that osteoblast is in implant surface Apposition growth.

In the 1960s, professor Branemark proposes Integrated implant concept, have for the success or not of planting body very big It influences.There are many factor for influencing Integrated implant, and wherein the surface property of planting body is particularly important, it has also become research emphasis in recent years. At present clinically, widely used dental implant has coarse surface substantially, compared with the planting body of smooth surface, has quickly Integrated implant and long-term clinical dental implant success rate.Therefore, the research and development of the planting body of surface roughening are always Dental implantion One of core direction of body field of surface treatment.

Following three categories are broadly divided into about implant surface processing at present:

(1) surface addition process: as titanium starches spraying (titanium plasma spray, TPS), hydroxyapatite coating layer (HA), calcium phosphate coating, biological coating etc..The planting body handled by surface addition process have good biocompatibility and Bioactivity is conducive to the synosteosis with implant surface early stage, but long-time stability are poor, and it is molten that the later period is easy to appear coating Solution and disbonding phenomenon.The outer general trend to the research and development of surface addition process of Now Domestic is declined.

(2) surface oxidation method: anodizing (anodic oxidation, AD), micro-arc oxidation (micro-arc Oxidation, MAO).Surface oxidation method is to change the configuration of surface of titanium by electrolysis using acid solution as electrolyte, at Point and crystal structure, keep implant surface coarse, and form certain thickness oxidation tunic.

(3) surface subraction: such as bulky grain sandblasting aciding (sandblasting with largegrit and Acid-etching, SLA), it can absorb media grit blast (resorbable blast media, RBM), laser treatment (laser Treatment) etc..

Judging from the current situation, surface addition process because long-time stability it is poor, later period coating dissolution and disbonding, now Research tendency is declined.Surface oxidation method is because superficial film is difficult to control, required for needing multiple steps just and capable of obtaining Film layer, the technological parameter for needing to control is more, and technique is extremely complex, and long-time stability need to be investigated.In general, surface subtracts Bulky grain sandblasting aciding in method is of relatively low cost, and by this processing mode, not only remains the diameter of sandblasting formation 20~60 μm of level-one pits, and 2~6 μm of second level pits of diameter of acid etching formation are increased, it forms unique cellular Roughing in surface form, level-one pit are conducive to the attachment of osteocyte, and second level pit can stimulate bone cell proliferation to break up, be conducive to Synosteosis is formed.Clinic confirms that SLA can shorten time dental implant-synosteosis time to 6 weeks.

Although SLA method has many good qualities, current study show that, it, can by increasing the surface hydrophilic performance of planting body Further reduce dental implant-synosteosis time.Hydrophilic implant surface becomes the hot spot researched and developed now.Wherein, hydrophilic plantation Body includes the SLActive planting body that Straumann company in 2004 releases, the INICELL that Thommen company in 2011 releases Planting body.The modified development trend of next-generation implant surface is had become for the hydrophilic modifying of rough surface at present.

CN1546187A discloses the method for improving medical metal material bioactivity, passes through differential arc oxidation, plasma The preparation of the technologies such as spraying has both antibacterial and active surface, realizes biological sealing.Several method used by the invention is due to applying Layer is too thick, there is the risk peeled off for a long time；In addition lower to the control precision of coating structure, ingredient.

CN104911558A discloses a kind of method that dental implant surface is modified, utilizes plasma immersion and ion implantation Method nail on preparation in tooth and have both antibacterial and active surface.The technology can reach very in structure, the control precision of ingredient High level, still, the disadvantage is that charge velocity is lower, the processing time is longer, therefore preparation cost is higher；In addition this method makes Metal injects element (Ag, Zn etc.) and there is uncertainty to the long-term influence of human body.

There are many method for improving implant surface performance, and wherein hydrophilicity rises to one of main research hotspot.

In physiological conditions, oxidation film and surface microscopic knot that the wetability of implant surface is mainly formed by its surface Structure, surface roughness codetermine, which can be compatible with protein and bone mineral.And it improves hydrophily and can be enhanced The reciprocation of implant surface and surrounding biologic environment directly affects the surface free energy of planting body, and surface is free An important factor for being protein and cell absorption again.But the titania surface performance of high activity is unstable, if lacked Special storage or protection, the surface are easily absorbing hydrocarbon and are contaminated, and reduce its hydrophily and bioactivity.

Therefore, how to keep hydrophilic surface is a key of clinical application steadily in the long term.These measures are specific The problems such as changing in application process there is transport and using more complicated, surface impurity ingredient introducing and microstructure.Therefore, Need a kind of more effectively holding hydrophilic method of implant surface.

Summary of the invention

In order to solve planting body performance hydrophily and the poor defect of stability existing in the prior art, mesh of the invention Be provide a kind of raising implant surface hydrophilic treatment process, i.e., planting body surface carry out SLA processing after, Alkali heat-treatment and plasma oxidation processing are then carried out, the MgCl of certain pH value is finally immersed in₂、CaCl₂It is molten with the mixing of NaCl In liquid, so that hydrophily is maintained.

Implant surface prepared by the present invention can not only improve the mechanical interlock of planting body and bone tissue, promote life The suction-operated of object bioactive molecule and cell, is conducive to the adherency proliferation of cell, while also improving its surface energy and wetability, The initial stage synosteosis speed for accelerating planting body, realizes quick Integrated implant.Hydrophily control method of the present invention is by surface topography and liquid Body impregnates common ensure and realizes.

The present invention is achieved through the following technical solutions:

A kind of planting body hydrophilic surface treatment process, comprising the following steps:

(1) planting body after cleaning successively sandblasting and acid etching: is subjected to blasting treatment and acid etching；

(2) alkali heat-treatment: the planting body after acid etching is placed in lye, is heated, cleaning, for use；

(3) plasma oxidation is handled: to the planting body radio frequency plasma after alkali heat-treatment, plasma oxidation processing is carried out, It is stand-by after cooling；

(4) hydrophilic treated: extreme trace cleaning is carried out to plasma oxidation treated planting body, is then directly immersed in MgCl₂、 CaCl₂It is impregnated in the mixed solution of NaCl.

Preferably, step (1) cleaning specifically: planting body is successively passed through Micro90 cleaning agent cleaning 20~ 50min, tap water rinse 1~5min and 10~40min of purified water ultrasonic cleaning.

Preferably, step (1) blasting treatment specifically: using white fused alumina or titanium oxide to the plantation body surface after cleaning Face carry out blasting treatment, wherein compressed air pressure be 2~6bar, spray distance be 50~150mm, blast time be 5~ 60s；The mesh number of white fused alumina or titanium oxide is 30~100 mesh；Acid etching specifically: the planting body after blasting treatment is placed in acid Acid etching is carried out in erosion liquid, the pickling solution presses volume by 49~98wt% sulfuric acid, 18~36wt% hydrochloric acid and deionized water Than (2~4): (1~4): (2~5) composition；The temperature of the acid etching is 50~100 DEG C, and etching time is 10~60min. Preferably, the acid etching specifically: the planting body after blasting treatment is placed in pickling solution and carries out acid etching, the acid Lose liquid by 49~98wt% sulfuric acid, 18~36wt% hydrochloric acid and deionized water by volume (2~4): (1~4): (2~5) group At；The temperature of the acid etching is 50~100 DEG C, and etching time is 10~60min.

Preferably, lye described in step (2) is the NaOH solution of 3~10mol/L, described to be heated to be at 50~80 DEG C Heat 10~60min.

Preferably, the condition of the plasma oxidation are as follows: Ar/O₂Flow-rate ratio is 10sccm/10sccm, and radio-frequency power is 200~500W, Dc bias -100~-500V, oxidization time 0.5-2h.

The extreme trace cleaning specially successively passes through purifying 1~5min of water spray, purified water is cleaned by ultrasonic 5~30min, pure Change 5~30min of water ultrasonic cleaning, Micro90 cleaning solution is cleaned by ultrasonic 20~50min, purified water rinses 1~5min and purifying 10~40min of water ultrasonic cleaning.

Preferably, the MgCl₂、CaCl₂Mass concentration with NaCl mixed solution is 0.5~3.0%, wherein MgCl₂、 CaCl₂Molar ratio with NaCl is (1~5): (2~4): 1.

Preferably, the MgCl₂、CaCl₂PH value with NaCl mixed solution is≤6, with this condition, not only makes to plant The hydrophily of body is preferable, and can make maintaining a long-term stability property of hydrophily.

Beneficial effects of the present invention:

(1) selection white fused alumina carries out blasting treatment to planting body, and it is high, non-friable that white fused alumina hardness height, intensity is utilized Characteristic is not likely to produce residual and pollution after sandblasting, can obtain level-one pit of the size at 20~60 μm.

(2) present invention is that hydrochloric acid and sulfuric acid mixed acid are handled with acid etching, and corrosion of the mixed acid to titanium is utilized Effect, provides good sandblasting dental implant surface pattern, so that the characteristic of good rough surface is presented in dental implant, so The interface bond strength of dental implant bone junction can be improved, to solve clinical problem existing for dental implant synosteosis aspect, Such as the problems such as implant neck bone resorption.The sulfuric acid of 49~98wt% and the concentration of hydrochloric acid of 18%~36wt% match acid etching effect Ideal, after the acid etching after proportion optimizing, implant surface forms uniform honeycomb second level pit after acid etching, Second level pit pattern has good uniformity, and is better than market mainstream planting body pattern, average-size is about 2~6 μm, adjacent several pits Nested structure is formed, osteoblast attachment and subsequent Proliferation, Differentiation is more conducive to, promotes synosteosis.

(3) present invention carries out the synergistic effect of alkali heat-treatment and plasma oxidation processing after SLA, wherein by alkali heat Implant surface honeycomb second level pit becomes round blunt that treated and uniformly, after being handled using plasma oxidation, surface Honeycomb second level dimple size further deepen and expand, it is finer and close and uniform, it is this synergistic effect so that side of the present invention Method treated implant surface has better surface texture, multistage hole configurations, higher surface energy.Surface roughness Ra has optimal bone guided at 1~4 μm, and planting body and bone tissue bond strength are high.

(4) in addition, the implant surface after alkali heat-treatment is due to having the formation of the presence of hydroxyl and surface more The careful structure of round blunt, so that the thin film of titanium oxide that next plasma oxidation processing is formed is easier and implant surface knot It closes, binding force is also relatively stronger, and this synergistic effect be combineding with each other can promote implant surface hydrophilic more stable.

(5) treated planting body is immersed the MgCl for regulating pH value≤6 by the present invention₂、CaCl₂With NaCl mixed solution In, it is contacted due to having completely cut off air with the direct of planting body, therefore it is able to maintain its hydrophilic long-time stability, to be conducive to protect The bioactivity of implant surface is held, the blood compatibility of planting body can be increased, and then improve the adherence rate of osteoblast, it is bright The aobvious proliferation and differentiation for promoting osteoblast, has positive effect for synosteosis；In addition, due to MgCl₂MgCl in solution₂It can water Solution, at faintly acid, makes the CaCl in mixed solution in this way₂It is not easily formed sl. sol. Ca (OH)₂, avoid it rotten, this salt is molten Synergistic effect between liquid is conducive to the hydrophilic steady in a long-term of planting body.

(6) state of charge of implant surface plays an important role in protein absorption, at physiological ph, TiO₂Surface band Negative electrical charge, Ca²⁺And Mg²⁺It, can be in negatively charged TiO for bivalent positive ion₂Surface and protein absorption in as connection from Son, thus be conducive to the absorption of albumen, therefore MgCl₂、CaCl₂Mixed solution with NaCl can increase as storage solutions to skeletonization The absorption of cell and protein.

(7) present invention process process is fairly simple, is suitble to commercially produce.

Detailed description of the invention

Fig. 1 is that the dental implant SEM after 1 gained acid etching of embodiment schemes (× 3000 times).

Fig. 2 is that the dental implant SEM after 1 gained acid etching of embodiment schemes (× 1500 times).

Fig. 3 is the surface roughness of the dental implant after 1 gained acid etching of embodiment.

Fig. 4 is MgCl of the 1 gained planting body of embodiment in different pH value₂、CaCl₂Treated with the mixed solution of NaCl Surface contact angle, wherein value=5 A:pH；Value=6 B:pH；Value=7 C:pH；Value=8 D:pH；Value=9 E:pH.

Fig. 5 is MgCl of the 1 gained planting body of embodiment in different pH value₂、CaCl₂Treated with the mixed solution of NaCl The tendency chart of surface contact angle.

Fig. 6 is that the cell of 3 gained TA4 planting body sample (B) of 4 gained TA4 planting body sample (A) of embodiment and comparative example is glutinous Attached result.

Fig. 7 is the optical microscopy (multiplying power x25) of 3 gained planting body (B) of 4 gained planting body (A) of embodiment and comparative example Photo.

Specific embodiment

In order to make the content of the present invention more clearly understood, right below according to specific embodiment and in conjunction with attached drawing The present invention is described in further detail.

One, the surface hydrophilicity treatment process of dental implant

Embodiment 1

In the present embodiment, the step of processing hydrophily TA4 dental implant is:

A. 25min, tap water rinse 2min successively will be cleaned by ultrasonic using Micro90 after the fine grinding of TA4 dental implant, it is pure Change water and cleans 20min, to clean up and oil removing, drying and processing later.

B. with the white fused alumina particle blasting treatment dental implant surface 10s of 30 mesh, blasting pressure in 0.3MPa, spray away from 10cm, until surface forms uniform grey, the porous structure for the 3 D stereo for forming dental implant surface, level-one pit diameter Between 20~60 μm.Micro90 ultrasonic cleaning 15min is successively carried out, tap water rinses purified water ultrasonic cleaning, dry.

C. the dental implant after sandblasting acid etching: is placed in 60wt%H₂SO₄, the mixed acid of 18wt%HCl and pure water it is molten In liquid, wherein 60wt%H₂SO₄, 10wt%HCl and pure water volume ratio be 3:3:4,75 DEG C of heating water baths handle 20min.It takes out Purified water is rinsed well afterwards.Dental implant surface is set to form the second level pit reduced step by step, wherein second level pit diameter is in 2~6 μ Between m.

D. alkali heat-treatment: the planting body after acid etching is placed in the NaOH solution of 4mol/L, at 50 °C plus Hot 20min, is cleaned by ultrasonic 10min with dehydrated alcohol and deionized water again after taking-up respectively.

E. the planting body after alkali heat-treatment is subjected to plasma oxidation, Ar/O₂Flow-rate ratio is 10sccm/10sccm, radio frequency Power is 250W, Dc bias -500V, oxidization time 1h, and cooling is stand-by.

F. finally the dental implant after plasma oxidation is successively cleaned by ultrasonic by purifying water spray 3min, purified water 20min, purified water ultrasonic cleaning 20min, Micro90 cleaning solution ultrasonic cleaning 30min, tap water rinse 3min and purified water Ultrasonic 30min.

G. hydrophilic treated: by the dental implant after cleaning, it is directly immersed in the MgCl of pH value=5,6,7,8 and 9₂、CaCl₂With It is impregnated in the mixed solution of NaCl 28 days, wherein the mass concentration of mixed solution is 0.9%, MgCl₂、CaCl₂With mole of NaCl Than for 5:2:1；The pH value of mixed solution is adjusted with the HCl solution of 1mol/L and the NaOH solution of 1mol/L.

The SEM figure of dental implant after acid etching is as depicted in figs. 1 and 2, it can be seen from the figure that implant surface is in Uniform honeycomb second level pit, planting body second level pit pattern uniformity and compactness are good, are better than market mainstream planting body Pattern, average-size are 2~6 μm, and adjacent several pits form nested structures, are more conducive to osteoblast attachment and subsequent Proliferation, Differentiation promotes synosteosis.

The roughness test result of planting body after gained acid etching is as shown in figure 3, its surface roughness Ra is 1.43 ± 0.158 μm, this roughness has optimal bone guided, so that planting body and bone tissue bond strength are more preferable.

Above-mentioned hydrophily treated dental implant sample is subjected to contact angle test, as shown in Figure 4 and Figure 5, Ke Yifa Existing, pH value changes to 9 from 5, and contact angle detection result is at 5 ° hereinafter, belong to super hydrophilic scope；Low ph value solution (pH value≤ 6) sample and in higher ph solution (pH value >=8) impregnated, moistened surface spreading rate is faster, it is seen that compares different pH value Solution impregnates sandblasting acid etching sample, it can be found that pH value≤6 or >=8, surface wettability is performed better than.

Extend above-mentioned dental implant in the MgCl of pH value=5,6,7,8 and 9₂、CaCl₂It is impregnated in the mixed solution of NaCl Time, test its contact angle, it is as a result as follows:

Table 1

As shown in Table 1, when impregnating 28 days in mixed solution, pH value≤6 or >=8, surface wettability is performed better than, i.e., Hydrophilic sex expression is preferable, but with the extension of soaking time, under neutral and alkaline condition, implant surface hydrophily becomes Difference, and in acid condition, planting body is still able to maintain preferable hydrophily, further illustrates MgCl₂、CaCl₂It is mixed with NaCl molten In liquid, MgCl₂The faintly acid being hydrolyzed into makes the CaCl in mixed solution₂It is not easily formed sl. sol. Ca (OH)₂, avoid its change Matter, the hydrophily that the synergistic effect between this salting liquid promotes planting body being capable of maintaining a long-term stability property.

Embodiment 2

A. 20min, tap water rinse 5min successively will be cleaned by ultrasonic using Micro90 after the fine grinding of TA4 dental implant, it is pure Change water and cleans 10min, to clean up and oil removing, drying and processing later.

B. with the white fused alumina particle blasting treatment dental implant surface 5s of 50 mesh, blasting pressure in 0.2MPa, spray away from 5cm, Uniform grey is formed to surface, the porous structure for the 3 D stereo for forming dental implant surface, level-one pit diameter is 20 Between~60 μm.Micro90 ultrasonic cleaning 15min is successively carried out, tap water rinses purified water ultrasonic cleaning, dry.

C. the dental implant after sandblasting acid etching: is placed in 98wt%H₂SO₄, the mixed acid of 36wt%HCl and pure water it is molten In liquid, wherein 98wt%H₂SO₄, 36wt%HCl and pure water volume ratio be 2:1:2,50 DEG C of heating water baths handle 60min.It takes out Purified water is rinsed well afterwards.Dental implant surface is set to form the second level pit reduced step by step, wherein second level pit diameter is in 2~6 μ Between m.

D. alkali heat-treatment: the planting body after acid etching is placed in the NaOH solution of 3mol/L, at a temperature of 60 DEG C plus Hot 60min, is cleaned by ultrasonic 10min with dehydrated alcohol and deionized water again after taking-up respectively.

E. the planting body after alkali heat-treatment is subjected to plasma oxidation, Ar/O₂Flow-rate ratio is 10sccm/10sccm, radio frequency Power is 200W, Dc bias -100V, oxidization time 2h, and cooling is stand-by.

F. finally the dental implant after plasma oxidation is successively cleaned by ultrasonic by purifying water spray 1min, purified water 5min, purified water ultrasonic cleaning 30min, Micro90 cleaning solution ultrasonic cleaning 20min, tap water rinses 1min, purified water surpasses Sound wave rinses 10min.

G. hydrophilic treated: by the dental implant after cleaning, it is directly immersed in the MgCl of pH value=5₂、CaCl₂With the mixing of NaCl It is impregnated in solution 28 days, wherein the mass concentration of mixed solution is 0.5%, MgCl₂、CaCl₂Molar ratio with NaCl is 1:1:1.

Embodiment 3

In the present embodiment, the step of processing hydrophily TC4 dental implant is:

A. 50min, tap water rinse 1min successively will be cleaned by ultrasonic using Micro90 after the fine grinding of TC4 dental implant, it is pure Change water and cleans 40min, to clean up and oil removing, drying and processing later.

B. with the white fused alumina particle blasting treatment dental implant surface 60s of 100 mesh, blasting pressure in 0.6MPa, spray away from 15cm, until surface forms uniform grey, the porous structure for the 3 D stereo for forming dental implant surface, level-one pit diameter Between 20~60 μm.Micro90 ultrasonic cleaning 15min is successively carried out, tap water rinses purified water ultrasonic cleaning, dry.

C. the dental implant after sandblasting acid etching: is placed in 49wt%H₂SO₄, the mixed acid of 18wt%HCl and pure water it is molten In liquid, wherein 49wt%H₂SO₄, 18wt%HCl and pure water volume ratio be 4:4:5,100 DEG C of heating water baths handle 10min.It takes Purified water is rinsed well after out.So that dental implant surface is formed the second level pit that reduces step by step, wherein second level pit diameter 2~ Between 6 μm.

D. alkali heat-treatment: the planting body after acid etching is placed in the NaOH solution of 10mol/L, at a temperature of 80 DEG C plus Hot 10min, is cleaned by ultrasonic 10min with dehydrated alcohol and deionized water again after taking-up respectively.

E. the planting body after alkali heat-treatment is subjected to plasma oxidation, Ar/O₂Flow-rate ratio is 10sccm/10sccm, radio frequency Power is 500W, Dc bias -200V, oxidization time 0.5h, and cooling is stand-by.

F. finally the dental implant after plasma oxidation is successively cleaned by ultrasonic by purifying water spray 5min, purified water 5min, purified water ultrasonic cleaning 5min, Micro90 cleaning solution ultrasonic cleaning 50min, tap water rinses 5min and purified water is super Sound wave rinses 40min.

G. hydrophilic treated: by the dental implant after cleaning, it is directly immersed in the MgCl of pH value=5₂、CaCl₂With the mixing of NaCl It is impregnated in solution 28 days, wherein the mass concentration of mixed solution is 1.2%, MgCl₂、CaCl₂Molar ratio with NaCl is 1:2:4.

Embodiment 4

A. 50min, tap water rinse 1min successively will be cleaned by ultrasonic using Micro90 after the fine grinding of TA4 dental implant, it is pure Change water and cleans 40min, to clean up and oil removing, drying and processing later.

D. alkali heat-treatment: the planting body after acid etching is placed in the NaOH solution of 6mol/L, at a temperature of 70 DEG C plus Hot 30min, is cleaned by ultrasonic 10min with dehydrated alcohol and deionized water again after taking-up respectively.

E. the planting body after alkali heat-treatment is subjected to plasma oxidation, Ar/O₂Flow-rate ratio is 10sccm/10sccm, radio frequency Power is 350W, Dc bias -300V, oxidization time 1.5h, and cooling is stand-by.

G. hydrophilic treated: by the dental implant after cleaning, it is directly immersed in the MgCl of pH value=5₂、CaCl₂With the mixing of NaCl It is impregnated in solution 28 days, wherein the mass concentration of mixed solution is 3.0%, MgCl₂、CaCl₂Molar ratio with NaCl is 4:2:1.

Comparative example 1

Step D in embodiment 4 is saved, other steps and parameter are the same as embodiment 4.

Comparative example 2

Step E in embodiment 4 is saved, other steps and parameter are the same as embodiment 4.

Comparative example 3

By " the MgCl in embodiment 4 in step G₂、CaCl₂With the mixed solution of NaCl " it is substituted for " CaCl₂With NaCl's Mixed solution ", " MgCl₂、CaCl₂Molar ratio with NaCl is that 5:2:1 " is substituted for " CaCl₂With the molar ratio of NaCl be 2:1 " its His step and parameter are the same as embodiment 4.

Comparative example 4

Step D in embodiment 4 and step E are saved, other steps and parameter are the same as embodiment 4.

Two, long-time stability are tested

To implement 1~4 and 3 gained planting body of comparative example progress contact angle test, test condition: vacuum drying, test are situated between Matter: ultrapure water extends soaking time of the planting body for implementing 1~4 and comparative example 3 in the storage solutions of hydrophilizing treatment step, Then it takes out respectively and carries out contact angle test, test result is as shown in table 2:

Table 2

Embodiment 2~4 can be seen that the extension with soaking time, MgCl from table 2₂、CaCl₂It is molten with the mixing of NaCl The hydrophilicity of the planting body stored in liquid accesses preferable holding, and with soaking time in 3 gained planting body of comparative example Extension, hydrophily becomes worse and worse, and stability is poor.Illustrate MgCl₂、CaCl₂Be conducive to plant with the mixed solution of NaCl The hydrophily of implant keeps its long-time stability；It may be due to MgCl₂MgCl in solution₂It can hydrolyze, at faintly acid, make in this way CaCl in mixed solution₂It is not easily formed sl. sol. Ca (OH)₂, avoid it rotten, the synergistic effect between this salting liquid has Conducive to the hydrophilic steady in a long-term of planting body.

Embodiment 2~4 and 1 result of comparative example can be seen that from table 2, not have alkali heat-treatment before plasma oxidation processing This step, so that the hydrophilic stability of 1 gained planting body of comparative example becomes poor (relative to 2~4 gained plantation of embodiment The stability of body), illustrate the implant surface after alkali heat-treatment due to having the formation of the presence of hydroxyl and surface more The careful structure of round blunt, so that the thin film of titanium oxide that next plasma oxidation processing is formed is easier and implant surface knot It closes, binding force is also relatively stronger, and this synergistic effect be combineding with each other can promote implant surface hydrophilic more stable.

Three, cell adhesion is tested

By the pure titanium implant sample that embodiment 4 and 3 technique of comparative example are surface-treated pure titanium sheet, to two kinds Pure titanium implant sample carries out cell adhesion experiment respectively, and steps are as follows:

A.PBS is cleaned cell 2 times；

B.4% paraformaldehyde room temperature fixes 10 minutes, and PBS is cleaned cell 2 times；

C.0.1%TritonX-100 room temperature 7min, PBS are cleaned cell 2 times；

D. the FITC- phalloidine room temperature that 5 μ g/ml are added dyes 30 minutes, and PBS is cleaned cell 3 times；

E.DAPI contaminates nucleus 10 minutes, and 37 DEG C, PBS is cleaned cell 3 times；Excessive moisture is sucked, fluorescence mounting liquid is added, is covered It is observed under upper coverslip, fluorescence or Laser Scanning Confocal Microscope；Or directly with the fluorescence mounting fluid-tight piece containing Dapi.

It is as shown in Figure 6 that embodiment 4 and 3 gained pure titanium implant sample cell of comparative example stick result, it can be seen that implements The adherent cell of 4 gained pure titanium implant sample of example sprawls that state is good, and cytoskeleton is clear, and it is more to stretch out pseudopodium；And 3 institute of comparative example Obtaining pure titanium implant sample adherent cell is in spindle shape, and cytoskeleton is not good enough, it is few compared with the former to stretch out pseudopodium, it was demonstrated that 4 institute of embodiment It obtains pure titanium implant and 3 gained pure titanium implant of comparative example is better than to the adhesion effect of cell.

Four, Osseointegrated implants are tested

By 1~4 gained sample of embodiment 4 and comparative example, zoopery is carried out respectively, the specific steps are as follows:

A. experimental animal prepares: 11 healthy adult male Labrador Retrievers of selection, and dog age 26-30 months, weight 25kg- 30kg.Experimental animal pulls out lower jaw bilateral first and second, two premolar teeths and first molar in advance, clears up art area, sewing-up cut, art After give antibiotic 3d, conventional semi-liquid diet is fed, spare after 3 months.Experimental animal is randomly divided into 2 weeks groups by healing time It organizes for 4,4 weeks 4,8 weeks and organizes 3.

B. surgical procedure: the healing of experimental animal bilateral alveoli dentales mandibulae nest is good, and art area is smooth, without obvious bone ridge.Along alveolus Glutinous periosteum holostrome is cut on ridge top, turns over valve, exposure cheek, tongue side bone plate.Quasi- implantation area is smooth, positioning, reaming to 10mm, and implantation is real Apply 4 planting body of example 2 and comparative example 1~4 each 2.All experimental animals are implanted into 110 planting bodies altogether.Implantation depth is smooth And with coarse and intersection.Planting body primary stability is good, screws in cover screw fixture cover, non-embedded type sewing-up cut.Postoperative give disappears Scorching analgesic drug product.Conventional semi-fluid nursing.It is postoperative to inspect periodically and clean wound, prevent complication, cleans cover screw fixture cover.Experiment is dynamic Object was put to death in a manner of overdose of anesthesia at 2,4,8 weeks respectively by grouping.

C. histology mark is wooden standby and histologic analysis: the independent bone block comprising planting body is placed in 4% formalin It is fixed, graded ethanol dehydration, resin embedding.Casting row hard tissue slicing (Leica, SP1600, Nussboch, Germany), cuts Piece is with a thickness of 150-200 μm, and grinding polishes cloth polishing to 60-80 μm by hand.Histotomy row methylene blue-acid fuchsin dye Color carries out histologic analysis using standard light microscope.Sample is placed under optical microscopy and observes Histological Study, is used in combination 6.0 software of Image-Pro Plus analyzes planting body surrounding bone-planting body Percentage bound.Bone-planting body Percentage bound is defined as planting Body and the direct contact surface of bone account for the ratio of planting body total surface.Measurement bone-planting body Percentage bound range is implant neck Rough surface and smooth surface have a common boundary to the overall length on planting body top.

D. Histological evaluation: 4 gained planting body of embodiment and 3 gained planting body of comparative example are in different planting body Implantation Times Under optical microscopy (multiplying power x25) photo respectively as shown in fig. 7, to its histological appearance, and retouched respectively in conjunction with Implantation Time It states as follows:

It is unobvious that 2 weeks: 2 kind of planting bodies show under mirror the reaction of bone tissue difference, and a small amount of bone occurs in ridge top region It absorbs.Peri-implant direct bone contact is few, and the nearly body region bone new life that plants is unobvious, and osteoblast has no typical in flat Skeletonization group, there are newborn osteoid, thin vessels in a small amount of region, it is seen that mesenchymal cell mitotic figure.Osteoblast nuclear hyperchromatism is dashed forward Touching interconnects, basophilic stippling in cytoplasm.Spacing is shorter between basophilla fold line (reversal line), closely plantation side See osteoclast.

4 weeks: the basic bone contact of planting body occupied planting body overall length, is essentially new bone under mirror, new bone growth is active, and skeletonization is thin Born of the same parents are active, and thin vessels generate, and are osteoid layer under the osteoblast layer of area of new bone side, and bone mineralising interruption is clear.

8 weeks: freshman bone tissue is almost full in planting body screw thread, basophilla fold line is obvious, and osteoblast is few, in flat Shape, new vessels are few, and newborn mineralising bone has formed bone lacuna.Osteoid is hardly seen.Osteoclast has no.Bone trabecula is arranged with Sequence, new bone almost join together with old bone.

The results are shown in Table 3 for planting body Percentage bound (BIC) for the bone-of 1~4 gained planting body of embodiment 4 and comparative example:

Table 3

From table 3 it can be seen that bone knot of the hydrophily planting body of the preparation of embodiment 4 compared with planting body prepared by comparative example 1~4 Preferably, and after planting body implantation as time increases, the Percentage bound of planting body and bone is higher and higher, of the invention for the performance of conjunction rate Hydrophily Osseointegrated implants result is preferable.Therefore, hydrophilic surface modification technique provided by the invention is to planting body bone knot Closing has good facilitation.

What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art For, under the premise of not departing from inventive concept, various modifications and improvements can be made, these belong to protection of the invention Range.

Claims

1. a kind of hydrophilic treatment process of implant surface, which comprises the following steps:

(3) plasma oxidation is handled: to the planting body radio frequency plasma after alkali heat-treatment, plasma oxidation processing is carried out, it is cooling It is stand-by afterwards；

(4) hydrophilic treated: extreme trace cleaning is carried out to plasma oxidation treated planting body, is then directly immersed in MgCl₂、CaCl₂ It is impregnated in the mixed solution of NaCl.

2. the hydrophilic treatment process of a kind of implant surface according to claim 1, which is characterized in that step (1) institute State cleaning specifically: planting body is successively passed through to 20~50min of Micro90 cleaning agent cleaning, tap water rinses 1~5min and pure Change 10~40min of water ultrasonic cleaning.

3. the hydrophilic treatment process of a kind of implant surface according to claim 1, which is characterized in that step (1) institute State blasting treatment specifically: blasting treatment is carried out to the implant surface after cleaning using white fused alumina or titanium oxide, wherein compressing Air pressure is 2~6bar, and spray distance is 50~150mm, and blast time is 5~60s；The mesh number of white fused alumina or titanium oxide is 30~100 mesh；Acid etching specifically: the planting body after blasting treatment is placed in pickling solution and carries out acid etching, the acid Lose liquid by 49~98wt% sulfuric acid, 18~36wt% hydrochloric acid and deionized water by volume (2~4): (1~4): (2~5) group At；The temperature of the acid etching is 50~100 DEG C, and etching time is 10~60min.

4. the hydrophilic treatment process of a kind of implant surface according to claim 1, which is characterized in that in step (2) The lye is the NaOH solution of 3~10mol/L, described to be heated to be 10~60min of heating at 50~80 DEG C.

5. the hydrophilic treatment process of a kind of implant surface according to claim 1, which is characterized in that the plasma The condition of oxidation are as follows: Ar/O₂Flow-rate ratio is 10sccm/10sccm, and radio-frequency power is 200~500W, Dc bias -100~- 500V, oxidization time 0.5-2h.

6. the hydrophilic treatment process of a kind of implant surface according to claim 1, which is characterized in that the extreme trace is clear Wash specially successively by purifying 1~5min of water spray, purified water be cleaned by ultrasonic 5~30min, purified water ultrasonic cleaning 5~ 20~50min of 30min, Micro90 cleaning solution ultrasonic cleaning, purified water 1~5min of flushing and purified water ultrasonic cleaning 10~ 40min。

7. the hydrophilic treatment process of a kind of implant surface according to claim 1, which is characterized in that the MgCl₂、 CaCl₂Mass concentration with NaCl mixed solution is 0.5~3.0%, wherein MgCl₂、CaCl₂With the molar ratio of NaCl be (1~ 5): (2~4): 1.

8. the hydrophilic treatment process of a kind of implant surface according to claim 1, which is characterized in that the MgCl₂、 CaCl₂PH value with NaCl mixed solution is≤6.