CN105965154B

CN105965154B - A kind of biomedical titanium surface modifying method

Info

Publication number: CN105965154B
Application number: CN201610472643.5A
Authority: CN
Inventors: 梁春永
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-06-27
Filing date: 2016-06-27
Publication date: 2018-06-26
Anticipated expiration: 2036-06-27
Also published as: CN105965154A

Abstract

The invention belongs to the preparation fields of bio-medical material, provide a kind of preparation method of surface modification biological medical pure titanium.This method includes polishing, femtosecond laser processing and three steps of alkali process, step SBF immersions can also be carried out to further improve bioactivity, the surface texture that this method is prepared is able to maintain that original appearance during subsequent alkali process, and surface hydrophilic is changed by surface hydrophobicity, the integration ability of biomedical titanium material and bone tissue is improved, so as to be applied to hard tissue alternate material.

Description

A kind of biomedical titanium surface modifying method

Technical field

The invention belongs to the preparation fields of bio-medical material, concretely relate to a kind of surface modification biological medical pure The preparation method of titanium.

Background technology

Titanium and its alloy rely on its light weight, excellent specific strength, corrosion resistance and good mechanical property in tooth kind The application of implant, artificial bone, joint prosthesis, orthopedic steel plate etc. occupies leading position, becomes human body hard tissue substitute With the preferred material of restoration.There is good application on femtosecond laser processing titanium surface, but only pass through femtosecond in angiocarpy bracket Laser Processing has super-drainage structure without the surface of any post processing, is unfavorable for the growth of seeking connections with of osteoblast, and titanium and its Alloy is as bio-inert material, although having a good biocompatibility with bone, its ingredient and natural bone tissue are completely not Together, it is a kind of simple mechanically integrated between people's bone, influences using effect.

Alkali process can improve the bioactivity on titanium surface, Kim et al. and titanium and its alloy are put into 60 DEG C of alkali in high alkali liquid 1h is heat-treated at 600 DEG C again after processing for 24 hours, treated, and exemplar is immersed in SBF (simulated body fluid) after 4 weeks, and surface can be apparent The formation of osteoid apatite is induced, shows that the bioactivity through alkali heat-treatment exemplar increases.Chen et al. first pass through etc. from TiO is made in stainless steel and titanium surface in sub- spraying technology₂Coating, then by the TiO of spraying₂Coating is put into high alkali liquid at 80 DEG C Alkali process 48h, experiment prove that alkali process can also improve TiO₂Film layer induces the Forming ability of apatite layer.In recent years, there is research Titanium and its alloy are first carried out anodized by person, are carried out at alkali in NaOH solution again after forming cavernous structure on surface As a result reason proves that alkali process can equally effectively improve Forming ability of the apatite layer in material surface.

But traditional alkali process reaction time consumption, it usually needs 24 ~ 48 hours, some later stages needed high-temperature calcination, and can destroy The matrix pattern prepared early period, the raising of biological property are also limited.

Invention content

The purpose of the present invention aiming at it is above-mentioned the problem of provide it is a kind of utilize femtosecond laser carry out the pure titanium table of bio-medical Surface modification process is able to maintain that original appearance, and by surface with the surface texture that this method is prepared during subsequent alkali process It is hydrophobic to be changed into surface hydrophilic, the integration ability of biomedical titanium material and bone tissue is improved, so as to be applied to sclerous tissues Alternate material.

The pure titanium surface modifying method of bio-medical of the present invention includes the following steps：

(1) it polishes：Physics polishing is carried out successively to pure titanium exemplar（Such as polishing, sandblasting）And chemical polishing, and clean, dry It is dry；

(2) femtosecond laser is processed：Titanium base material after polishing is subjected to femtosecond laser processing, and clean, dry, is processed It is 1000Hz that parameter, which is frequency, and laser polarization direction is perpendicular to machine direction, and defocusing amount is 0 ~ 3000 μm during processing, power 50 ~ 500mw, sweep span are 20 ~ 150 μm, processing speed 0.8mm/s, and processing platform used is laser machined for sapphire femto-second System.

(3) alkali process：The pure titanium exemplar with micro nano surface structure of femtosecond laser processing gained is placed in boiling lye Middle processing 2 hours, wherein alkali process solution are NaOH KOH solution, clean and dry after alkali process, you can pure The bioactivity surface with micro-nano structure is obtained on titanium exemplar.

In addition, if think further to obtain the bioactivity surface covered with hydroxyapatite, it can also be by step（3）Institute The pure titanium exemplar obtained is placed in rich 1.5 times of SBF of sodium with being impregnated at 37 DEG C 7 days, changes within every two days a not good liquor, 1.5 times of the rich sodium The preparation method of SBF is at 37 DEG C, in strict accordance with sequence by 9.825g NaCl, 3.402g NaHCO₃, 0.5595gKCl, 0.4575g MgCl_2·6H₂O, 0.1065g Na₂SO₄, 0.402g Na₂HPO_4·7H₂O, 0.552g CaCl_2·2H₂O and 9.0855g Tris, which is added in deionized water, is configured to 1L solution, and ensures final pH stabilization 7.4.

Above-mentioned steps（1）In, chemical polishing solution is using the aqueous solution of ‰ acid fog inhibitor of HF and 0.02wt of 3wt%, polishing Time is 2min, required polishing area（mm²）With polishing fluid volume used（ml）Ratio be 10：1.

Above-mentioned steps（3）In, a concentration of 1~5mol/L of lye in molar ratio, optimal is 2 mol/L.

Above-mentioned steps（1）And step（2）In cleaning step be cleaned by ultrasonic three times, cleaning solution is followed successively by acetone, second Alcohol and deionized water, the time cleaned every time according to dirt and erosion slag type and content depending on, no longer than 10 minutes, example Such as, in polishing step, material surface is since the greasy dirt content that upstream wire cutting technology generates is more, the scavenging period of acetone Answer long enough, step（3）In only be cleaned by ultrasonic with deionized water.

After being handled using femtosecond laser machined parameters of the present invention, pure titanium sample surface can obtain the pattern of four types, Respectively pit shape structure, striated structure, island structure and convex stripe composite construction, corresponding femtosecond laser machined parameters As shown in table 1,

1 femtosecond laser machined parameters of table and the gained surface texture table of comparisons

	A	B	C	D
					Defocusing amount（µm）	0~200	200~1500	1000~2000	1500~3000
Spacing（µm）	20~50	50~150	50~100	30~100
					Laser power（mw）	50~300	50~200	300~500	50~300
Sweep speed（mm/s）	0.8	0.8	0.8	0.8
					Patterning	Pit shape structure	Striated structure	Island structure	Protrusion and striped composite construction

Biomedical titanium surface modifying method provided by the invention has the advantages that：

1st, the exemplar prepared after femtosecond laser processing surface texture during subsequent alkali process is able to maintain that original appearance.

2nd, the exemplar prepared after femtosecond laser processing is changed into surface hydrophilic after alkali process by surface hydrophobicity.

3rd, after alkali process, high-temperature calcination technique is eliminated with respect to other methods for exemplar prepared by this method.

Description of the drawings：

Fig. 1 is 1 gained sample surface field emission scanning electron microscope figure of embodiment.

Fig. 2 is 1 gained sample surface atomic force microscopy diagram of embodiment.

Fig. 3 is the surface Flied emission scanning electron microscope (SEM) photograph after 1 gained exemplar alkali process of embodiment.

Fig. 4 is the surface hydrophilicity comparison before and after 1 gained exemplar alkali process of embodiment.

Fig. 5 is 2 gained sample surface field emission scanning electron microscope figure of embodiment.

Fig. 6 is 2 gained sample surface atomic force microscopy diagram of embodiment.

Fig. 7 is the surface Flied emission scanning electron microscope (SEM) photograph after 2 gained exemplar alkali process of embodiment.

Fig. 8 is the surface hydrophilicity comparison before and after 2 gained exemplar alkali process of embodiment.

Fig. 9 is 3 gained sample surface field emission scanning electron microscope figure of embodiment.

Figure 10 is 3 gained sample surface atomic force microscopy diagram of embodiment.

Figure 11 is the surface Flied emission scanning electron microscope (SEM) photograph after 3 gained exemplar alkali process of embodiment.

Figure 12 is the surface hydrophilicity comparison before and after 3 gained exemplar alkali process of embodiment.

Figure 13 is 4 gained sample surface field emission scanning electron microscope figure of embodiment.

Figure 14 is 4 gained sample surface atomic force microscopy diagram of embodiment.

Figure 15 is the surface Flied emission scanning electron microscope (SEM) photograph after 4 gained exemplar alkali process of embodiment.

Figure 16 is the surface hydrophilicity comparison before and after 4 gained exemplar alkali process of embodiment.

Figure 17 is impregnated for present invention gained exemplar in 1.5 times of SBF, the power spectrum and X ray of Surface Creation hydroxyapatite Diffraction testing result.

Specific embodiment party example

Embodiment 1

（1）Pure titanium exemplar (specification 10mm*10mm*1mm) is selected to carry out physics polishing and chemical polishing successively：

Physics polishes：Polishing 4 times, sand paper mesh number is followed successively by 800,1000,1500 and 2000.

Chemical polishing：Polishing fluid uses the aqueous solution of ‰ perfluoro octyl sulfonic acid potassium of 200ml HF containing 3wt% and 0 .02wt, Polishing time is 2min, then submerges ultrasonic cleaning 3 minutes, drying entirely with acetone, ethyl alcohol and deionized water successively；

（2）Femtosecond laser is processed：Using the pure titanium exemplar after polishing, machined parameters are：Defocusing amount 0um, sweep span 30 Um, power 100mw, 0 .8mm/s of sweep speed, directional velocity is perpendicular to light polarization direction.Then use successively at room temperature Acetone, ethyl alcohol and deionized water are cleaned by ultrasonic, and acetone cleans 1 minute, and ethyl alcohol and deionized water are respectively cleaned 2 minutes and dried. Surface image is observed under transmitting scanning electron microscope, sees Fig. 1, gained sample surface is continuous pit shape structure, the ditch of pit composition Well width is about 25um, is separated between two groups of pits by one group of ridge.Atomic force microscope 3-D view also confirms well in Fig. 2 The structure.

（3）Alkali process：The pure titanium exemplar with micro nano surface structure of femtosecond laser processing gained is placed in boiling NaOH Handled 2 hours in solution, after deionized water clean and dry.For Fig. 3 as it can be seen that after soda boiling, specimen surface maintains step 2 Obtained structure.After Fig. 4 shows alkali process, contact angle is reduced to 14.5 ° by 146.7 °, it can be seen that surface is changed by hydrophobic It is hydrophilic.

（4）Prepared exemplar is placed in 37 DEG C of 1.5 times of SBF and impregnated, changed a not good liquor within every 2 days, take out exemplar after two weeks, It is gently rinsed and then is dried at room temperature for pure water.

Embodiment 2 ~ 4 in the same manner as shown in Example 1, only changes the parameter of Laser Processing.Design parameter is shown in Table 2

Table 2

Embodiment	Defocusing amount（um）	Sweep span（um）	Laser power (mw)	Sweep speed (mm/s)
					2	1000	100	50	0.8
3	1600	50	400	0.8
					4	2000	50	100	0.8

Fig. 5 ~ 8 show to have obtained striated structure in embodiment 2, will not change surface topography after the structure alkali process, and Water-wetted surface is become from hydrophobic surface.Fig. 9 ~ 12 show to have obtained island structure in embodiment 3, will not after the structure alkali process Change surface topography, and water-wetted surface is become from hydrophobic surface.Figure 13 ~ 16 show that protrusion and striped have been obtained in embodiment 4 answers Structure is closed, will not change surface topography, and water-wetted surface is become from hydrophobic surface after the structure alkali process.

Figure 17 shows pure titanium sample made from embodiment 1 ~ 4,1.5 times of SBF impregnate spherical substance that rear surfaces are newly formed into Row EDS and XRD（Figure 17）Analysis illustrates that processed exemplar has excellent phosphorus it is found that new forming material is hydroxyapatite Lime stone induced synthesis ability, i.e., good bioactivity.

Embodiment 5 ~ 26：In the same manner as shown in Example 1, change the defocusing amount of Laser Processing, sweep span, work( Rate, alkali process solution concentration, gained surface texture pattern are shown in Table 3, and hydrophily is all improved, and is omitted herein to exempt to repeat.

Table 3

Claims

1. a kind of biomedical titanium surface modifying method, it is characterised in that include the following steps：

(1) it polishes：Physics polishing and chemical polishing are carried out successively, and clean, dry to pure titanium exemplar；

(2) femtosecond laser is processed：Titanium base material after polishing is subjected to femtosecond laser processing, and clean, dry, machined parameters It is 1000Hz for frequency, laser polarization direction is perpendicular to machine direction, and defocusing amount is 0 ~ 3000 μm, and power is 50 ~ 500mw, is swept It is 20 ~ 150 μm, processing speed 0.8mm/s to retouch spacing, and processing platform used is sapphire femto-second laser-processing system；

(3) alkali process：The pure titanium exemplar with micro nano surface structure of femtosecond laser processing gained is placed in boiling lye Reason 2 hours, cleans and is dried after alkali process.

2. biomedical titanium surface modifying method according to claim 1, it is characterised in that the chemistry described in step (1) The polishing fluid used is polished as the aqueous solution of ‰ acid fog inhibitor of HF and 0.02wt of 3wt%, polishing time 2min, required throwing Light area（mm²）With polishing fluid volume used（ml）Ratio be 10：1.

3. biomedical titanium surface modifying method according to claim 1, it is characterised in that step（3）In, lye is NaOH KOH solution, a concentration of 1~5mol/L.

4. biomedical titanium surface modifying method according to claim 3, it is characterised in that concentration of lye is 2 mol/L.

5. biomedical titanium surface modifying method according to claim 1, it is characterised in that step（1）And step（2）In Cleaning step be cleaned by ultrasonic three times, cleaning solution is followed successively by acetone, ethyl alcohol and deionized water, the time cleaned every time according to Depending on the type and content of dirt and erosion slag, no longer than 10 minutes, step（3）In only be cleaned by ultrasonic with deionized water.

6. biomedical titanium surface modifying method according to claim 1, it is characterised in that include the following steps：

(2) femtosecond laser is processed：Titanium base material after polishing is subjected to femtosecond laser processing, and clean, dry, machined parameters It is 1000Hz for frequency, laser polarization direction is perpendicular to machine direction, and defocusing amount is 0 ~ 200 μm, and power is 50 ~ 300mw, is swept It is 20 ~ 50 μm, processing speed 0.8mm/s to retouch spacing, and processing platform used is sapphire femto-second laser-processing system；

7. biomedical titanium surface modifying method according to claim 1, it is characterised in that include the following steps：

(2) femtosecond laser is processed：Titanium base material after polishing is subjected to femtosecond laser processing, and clean, dry, machined parameters It is 1000Hz for frequency, for laser polarization direction perpendicular to machine direction, defocusing amount is 200 ~ 1500 μm, and power is 50 ~ 200mw, Sweep span is 50 ~ 150 μm, processing speed 0.8mm/s, and processing platform used is sapphire femto-second laser-processing system；

8. biomedical titanium surface modifying method according to claim 1, it is characterised in that include the following steps：

(2) femtosecond laser is processed：Titanium base material after polishing is subjected to femtosecond laser processing, and clean, dry, machined parameters Be 1000Hz for frequency, for laser polarization direction perpendicular to machine direction, defocusing amount is 1000 ~ 2000 μm, power for 300 ~ 500mw, sweep span are 50 ~ 100 μm, processing speed 0.8mm/s, and processing platform used is sapphire femto-second Laser Processing system System；

9. biomedical titanium surface modifying method according to claim 1, it is characterised in that include the following steps：

(2) femtosecond laser is processed：Titanium base material after polishing is subjected to femtosecond laser processing, and clean, dry, machined parameters It is 1000Hz for frequency, for laser polarization direction perpendicular to machine direction, defocusing amount is 1500 ~ 3000 μm, and power is 50 ~ 300mw, Sweep span is 30 ~ 100 μm, processing speed 0.8mm/s, and processing platform used is sapphire femto-second laser-processing system；

10. biomedical titanium surface modifying method according to claim 1, it is characterised in that further include step（4）：It will Step（3）The pure titanium exemplar of gained is placed in rich 1.5 times of SBF of sodium to be impregnated 7 days at 37 DEG C, changes a not good liquor within every two days, described The preparation method of rich 1.5 times of SBF of sodium is at 37 DEG C, in strict accordance with sequence by 9.825g NaCl, 3.402g NaHCO₃, 0.5595gKCl, 0.4575g MgCl_2·6H₂O, 0.1065g Na₂SO₄, 0.402g Na₂HPO_4·7H₂O, 0.552g CaCl_2· 2H₂O and 9.0855g Tris, which are added in deionized water, is configured to 1L solution, and ensures final pH stabilization 7.4.