CN105435305B - A kind of POROUS TITANIUM composite material and preparation method - Google Patents
A kind of POROUS TITANIUM composite material and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of POROUS TITANIUM composite material and preparation methods, belong to Metallic Functional Materials and technical field of polymer materials, it can efficiently solve in the method for adjustment parameter the growth in situ silver particles directly on porous Titanium base and carry albumen or carry the microballoon and POROUS TITANIUM combined shaping problem of drug.POROUS TITANIUM is first prepared using occupy-place stuffing process, selects ammonium hydrogen carbonate as pore creating material, pore-forming after being pre-sintered at 150 DEG C~180 DEG C is formed by vacuum-sintering, to obtain high porosity, and includes the porous Titanium base of a large amount of network-like perforation holes.And in conjunction with anodized, becoming existing macroscopic pores again has the multiple dimensioned pore structure POROUS TITANIUM of micropore.Silver particles are generated in porous Titanium base Central Plains position by photoreduction met hod again.Then the gelatine microsphere after selecting crosslinking is wrapped up by physical absorption as carrier and is loaded into bioactive molecule.It is mainly used for repairing human body hard tissue.
Description
Technical field:
The present invention relates to Metallic Functional Materials and technical field of polymer materials, especially that organizational project is multiple with drug
The technical field that release function combines.
Background technique:
POROUS TITANIUM is nontoxic, harmless and have preferable biocompatibility.By control technical arrangement plan product porosity with
Change its elasticity modulus, is conducive to tissue and grows into hole realization Integrated implant, and reach and body bone tissue or musculature
The purpose to match.In addition, the hole of POROUS TITANIUM connection is conducive to the transmission of human body fluid nutritional ingredient, thus it is widely used
In medical and health industry.
Ag, Cu and Zn are main metal antibacterial agent, wherein again the most significant with the antibacterial effect of silver, silver is a kind of tradition
Broad spectrum antimicrobial agent, effect is killed to most bacteriums.The cell wall and cell membrane of nearly all bacterium all have negative
Charge works as Trace Ag+When reaching microbial cell film, since the charges of different polarity are attracting, Ag+It is easy to by various bacteriums without selectively
Absorption, instead of the position of cell membrane surface cation, destroys the metabolism of film, the existence microenvironment disorder of bacterium is caused to lack of proper care,
Eventually lead to bacterial death.
Gelatin is natural high molecular material, nontoxic, good biocompatibility, biodegradable.Gelatine microsphere usually has very
High drugloading rate, and it is easy its degradation rate in human physiological environment.It is entered in body fluid when carrying medicine gelatine microsphere
When, it is swollen with cross-linked gelatin, gradually discharges wrapped up drug.Gelatine microsphere support drug with controlled release and stability it is good
The characteristics of, so that it is widely used in materia medica research field.For example, in the drug absorption and distribution of studying oral drug bearing microsphere
Aspect compares conventional ibuprofen oral preparation and carries the gelatine microsphere oral preparation of brufen, finds the blood of the latter's experimental rat
Slurry drug concentration is higher, and bioavilability is substantially better than conventional oral preparation.The present invention is to use the gelatine microsphere prepared
It is reloaded in POROUS TITANIUM in supporting bioactive molecule.Loading process carries out in a mild condition, is maintained and supports ingredient
Bioactivity, and it is made to realize control release at bone defect position, promotes osteocyte and tissue growth.
" the Porous Titanium Scaffold that " Surface and coatings technology " is delivered
Surfaces Modified with Silver Loaded Gelatin Microspheres and Their
Antibacterial Behavior " article supports research of the silver-colored simple substance for porous titanium material antibiotic property about gelatine microsphere.
Although the argentiferous porous titanium material of this report is able to achieve the antibacterial effect of early period, the wherein bio-compatible of argentiferous porous titanium material
Property is influenced by silver particles toxicity, lacks antibiotic property and bioactivity in view of POROUS TITANIUM itself, therefore the present invention is basic herein
Upper pass through introduces the relevant growth factor of osteocyte, and material not only realizes that the ability of antibacterial also contributes to improving the biofacies of material
Capacitive.
Summary of the invention:
The object of the present invention is to provide a kind of porous titanium composite materials, it can efficiently solve long-term antimicrobial efficiency and promote bone
The problem of cell and tissue growth.
It is a further object to provide a kind of preparation method of porous titanium composite material, it can efficiently solve with
The method of adjustment parameter growth in situ silver particles and load albumen or the microballoon and POROUS TITANIUM that carry drug directly on porous Titanium base
Combined shaping problem.
The purpose of the present invention is achieved through the following technical solutions: a kind of porous titanium composite material, has macroscopic pores
The porous Titanium base of diameter and micropore, silver particles on the porous Titanium base with growth in situ and is loaded with containing the bright of albumen
Glue microballoon generates oxidation film and the micropore on POROUS TITANIUM surface after anodic oxidation, the POROUS TITANIUM for constituting argentiferous load protein microsphere is multiple
Condensation material.
100 ± 5.8Mpa of compression strength of the porous titanium composite material, elasticity modulus are 1.5 ± 0.2Gpa, and bending is strong
Degree is 50 ± 2.4Mpa；POROUS TITANIUM porosity is 65 ± 5%, percent opening 75 ± 5%.
The porous titanium composite material belongs to hard tissue alternate material, the reparation as humerus, femur and dental implant.
Another object of the present invention is achieved through the following technical solutions: a kind of preparation of porous titanium composite material
Method, comprising the following steps:
Step 1: the preparation of porous Titanium base, takes titanium valve to mix with pore creating material ammonium hydrogen carbonate according to 1:1, it is 50 in pressure
Compression moulding under~100MPa；Molding blank is placed in pre-burning in sintering furnace, 150 are risen to by room temperature with the rate of 1 DEG C/min~
180 DEG C, 3~5h is kept the temperature, ammonium hydrogen carbonate is removed, forms the titanium sample of porous structure, the titanium sample after pre-burning is put into vacuum and is burnt
In freezing of a furnace, vacuum degree maintains 10-3~10-4Pa is warming up to 1100 DEG C~1300 DEG C with the rate of 5 DEG C/min, after keeping the temperature 2~4h
Furnace cooling is taken out spare up to porous Titanium base；
Step 2: the preparation of the multiple dimensioned porous Titanium base of pore structure selects anodic oxidation reactions using sulfuric acid as electrolyte,
Anodic oxidation is carried out to porous Titanium base, forms 1~5 μm of micropore after oxidation reaction on hole wall, obtains having both macro hole and micro-
The porous Titanium base of multiple dimensioned pore structure in hole；
Step 3: growth in situ silver particles on porous Titanium base, are immersed in nitric acid for porous Titanium base prepared by second step
1~3h in silver-colored solution, uses 1~3h of ultraviolet light after taking-up, vacuum drying obtains the porous titanium-based of growth in situ silver particles
Body, for use；
Step 4: the preparation of gelatine microsphere is 60 DEG C in environment temperature by atoleine and sorbester p17 in the ratio of 98:2
When after evenly mixing, be added dropwise in mutually synthermal aqueous gelatin solution and emulsify cooling 30min；When aqueous gelatin solution is cooled to
At 4 DEG C, the glutaraldehyde that 4ml concentration is 5%~25% is added and is crosslinked, the reaction time is 40min~1h, and acetone is then added
Water-oil separation is carried out, is finally alternately washed on vacuum filtration machine using acetone and dehydrated alcohol, it is micro- to obtain gelatin for freeze-drying
Ball saves；
Step 5: albumen is loaded into gelatine microsphere, the ratio for being 1:100 according to mass volume ratio, by gelatine microsphere point
It is dispersed in 24~48h in the protein liquid that concentration is 2%~5%, after taking-up under conditions of 2500~3500r/min, centrifuge washing
Twice, it is freeze-dried up to the gelatine microsphere of albumen is loaded into, saves；
Step 6: the gelatine microsphere containing albumen is loaded into the porous Titanium base of argentiferous, loading albumen obtained by the 5th step is taken
Gelatine microsphere be dispersed in ultrasound 20min in 2%~5% protein liquid and obtain the protein suspending liquid containing gelatine microsphere；By third step
The porous Titanium base of prepared argentiferous is placed in the gelatin solution that mass volume ratio is 1~5%, is taken out after impregnating 30min~1h
It is transferred in foregoing proteins suspension again, it is compound that the POROUS TITANIUM for carrying protein microsphere to get argentiferous is taken out and spontaneously dried after 24~48h
Material.
The voltage of the anodic oxidation reactions is 90~110V, and sulfuric acid concentration is 0.01M~0.1M, and the time is 1~3min.
The AgNO3Solution concentration is 0.001M~0.005M.
The albumen that the gelatine microsphere is loaded into is one of following protein: albumen (BMP), fibroblast occur for bon e formation
Growth factor (FGF), the raw sub- factor (TGF) of conversion or polypeptide.
Advantages and beneficial effects are compared with prior art:
(1) addition pore creating material method can control aperture and porosity by adjusting the proportion of pore creating material partial size and titanium valve,
If the ratio of 1:1 is selected to add pore creating material, the available pore structure for being suitable for bone tissue and growing into, 100~400 μ of aperture
M, porosity 60%~70%, percent opening 70%~80%.And further by the processing of anodic oxidation, in POROUS TITANIUM surface shape
At oxidation film and microcellular structure, the porous titanium material with multiple dimensioned pore structure is prepared, biocompatibility and bioactivity are aobvious
It writes and improves.
(2) it is used as macromolecule gelatine microsphere, bioprotein is not only wrapped up into inside microballoon, but also is adsorbed in microsphere surface,
Facilitate the release step by step of albumen or drug by this spatial distribution.Be loaded into the gelatine microsphere of drug at human lesion position or
Damaged part can stop the longer time, can extend the deenergized period of drug, by the size, that is, controllable medicine for adjusting microspherulite diameter
The velocity and time of object release.
(3) it prepares and is carried in albumen or the microballoon for carrying drug at other, the medicaments such as crosslinking agent used would generally destroy albumen
Or drug itself, so that its activity is damaged.The invention is able to maintain the activity of protein or other biological molecule, for human body by
The recovery for damaging position has positive facilitation.
(4) it is directed to different sclerous tissues' damage locations, the type of institute's indispensable protein may be different, compared to traditional side
Method, carry one or more bioactive molecules to the gelatine microsphere property of can choose of the invention and be loaded into porous Titanium base into
Row release.
(5) compared to other antibacterial agents, silver-colored bactericidal effect is more prominent, and silver particles can be steadily reduced more
On the Titanium base of hole, to realize Ag+Stable release.By regulating and controlling AgNO3Concentration can also regulate and control the load in porous Titanium base
Silver content.During release, initial stage can be discharged by microballoon gap, alleviate burst release；Although later period silver content is reduced, with
Microballoon is gradually degraded and is spread, and increases material and contacts with body fluid, is able to achieve long-term release effective sterilizing dosage.
(6) compared with the drug that traditional POROUS TITANIUM is loaded into, which plays long acting antibiotic and promotes sclerous tissues' growth
Double effects.The treatment that silver-colored antibacterial is loaded into after single sclerous tissues' implant surgery is not only solved, and gelatine microsphere is loaded into
Albumen have the function of promoting osteocyte and tissue growth.
It is micro- with gelatin after porous titanium composite material implantation by being loaded into bioactive molecule in gelatine microsphere
The degradation of ball and the circulation of body fluid, protein or bioactive molecule can control release at bone defect position, to induce, promote
Into the reparation and healing of damage location.This method can be by changing pore creating material NH4HCO3With the ratio of titanium valve, regulate and control POROUS TITANIUM
The elasticity modulus and mechanical strength of matrix, so as to avoid stress shadowing effect.Moreover, in conjunction with anodic oxidation in porous titanium-based
Body surface face forms oxide layer and microcellular structure obtains the porous titanium composite material of multiple dimensioned pore structure, to further increase material
The biocompatibility of active site and raising material that surface microballoon combines.
Detailed description of the invention
Fig. 1 is porous titanium composite material electromicroscopic photograph (100 times) of the invention
Fig. 2 is that porous titanium composite material of the invention is loaded into silver particles electromicroscopic photograph (500 times)
Fig. 3 is that porous titanium composite material of the invention carries silver-colored electromicroscopic photograph containing protein microsphere (100 times)
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment one
Step 1: the preparation of porous Titanium base
Titanium valve and pore creating material ammonium hydrogen carbonate is taken to mix according to 1:1 ratio, molding blank is set in the compression moulding at 50MPa
Enter sintering furnace, rises to 150 DEG C by room temperature with the heating rate of 1 DEG C/min, keep the temperature 3h, remove ammonium hydrogen carbonate, form porous structure；
Then the sample after pre-burning is put into vacuum sintering furnace, is warming up to 1200 DEG C with the heating rate of 5 DEG C/min, keep the temperature after 2h with
Furnace is cooling, and vacuum degree maintains 1.0 × 10-3Pa。
Step 2: the preparation of the multiple dimensioned porous Titanium base of pore structure
The sulfuric acid for selecting 0.1M is electrolyte, and voltage 90V, reaction time 1min carry out anode to porous Titanium base
Oxidation obtains having both the POROUS TITANIUM basis material in macro hole and micropore.
Step 3: growth in situ silver particles on POROUS TITANIUM basis material
Porous Titanium base prepared by second step is immersed in the AgNO that concentration is 0.001M31h in solution, it is ultraviolet after taking-up
Light irradiates 1h, is dried in vacuo the POROUS TITANIUM basis material to get growth in situ silver particles, for use.
Step 4: the preparation of gelatine microsphere
(1) Arlacel-80 of the atoleine and 1.5ml that take 70ml mixes equal in the case where environment temperature is 60 DEG C of water bath conditions
It is even.1g gelatin powder is dissolved in deionized water at the same temperature.
(2) 60 DEG C are kept, gelatin solution is instilled in the mixed liquor of atoleine and Arlacel-80 and is emulsified, after 30min
Rapid cooling emulsion is added the glutaraldehyde that 4ml concentration is 5% when emulsion temperature is 4 DEG C and is crosslinked, and the reaction time is
40min。
(3) after crosslinking is completed, the acetone that 30ml is added carries out water-oil separating, time 40min, finally using acetone and
Dehydrated alcohol is alternately filtered, is washed, and freeze-drying obtains gelatine microsphere, is saved.
Step 5: being loaded into BMP-2 albumen in gelatine microsphere
It takes 1mgBMP-2 protein dissolution in 10mlPBS, 0.1g gelatine microsphere is then added and impregnates for 24 hours, then 2500 revs/min
Twice, freeze-drying saves centrifuge washing to get the gelatine microsphere containing albumen.
Step 6: the gelatine microsphere containing albumen is loaded into the porous Titanium base of argentiferous
The gelatine microsphere containing BMP-2 albumen obtained by the 5th step and 2% protein liquid is taken to be made into gelatine microsphere albumen
Suspension, ultrasonic 20min.Argentiferous POROUS TITANIUM basis material prepared by third step is placed in the gelatin that mass volume ratio is 1%
It in solution, takes out and is transferred in aforementioned gelatine microsphere protein suspending liquid again after immersion 30min, take out afterwards for 24 hours and dry to get argentiferous
With the porous titanium composite material for carrying BMP-2 microballoon.
Embodiment two
This example is a part of identical as example, and institute's difference is:
Step 1: the preparation of porous Titanium base, takes titanium valve and pore creating material ammonium hydrogen carbonate to mix according to 1:1 ratio, in 80MPa
Lower compression moulding, is placed in sintering furnace for molding blank, rises to 165 DEG C by room temperature with the heating rate of 1 DEG C/min, keeps the temperature 4h, remove
Ammonium hydrogen carbonate is removed, porous structure is formed；Then the sample after pre-burning is put into vacuum sintering furnace, with the heating speed of 5 DEG C/min
Rate is warming up to 1200 DEG C, keeps the temperature furnace cooling after 3h, and vacuum degree maintains 1.0 × 10-3Pa。
Step 2: the preparation of the multiple dimensioned porous Titanium base of pore structure, selecting the sulfuric acid of 0.05M is electrolyte, and voltage is
100V, reaction time 2min carry out the porous Titanium base material that anodic oxidation obtains having both macro hole and micropore to porous Titanium base
Material.
Step 3: growth in situ silver particles on POROUS TITANIUM basis material, porous Titanium base prepared by second step is immersed in
Concentration is the AgNO of 0.0025M32h in solution, ultraviolet light 2h after taking-up are dried in vacuo to get growth in situ silver particles
POROUS TITANIUM basis material, for use.
Step 4: the preparation of gelatine microsphere, (1) takes the atoleine of 70ml and the Arlacel-80 of 1.5ml is in environment temperature
It is uniformly mixed under 60 DEG C of water bath conditions.1g gelatin powder is dissolved in deionized water at the same temperature.(2) 60 DEG C are kept,
Gelatin solution is instilled in the mixed liquor of atoleine and Arlacel-80 and is emulsified, rapid cooling emulsion after 30min, in cream
Change the glutaraldehyde that addition 4ml concentration is 15% when liquid temperature is 4 DEG C to be crosslinked, reaction time 50min.(3) crosslinking is completed
After, the acetone that 30ml is added carries out water-oil separating, and time 50min is finally alternately filtered using acetone and dehydrated alcohol and washed
It washs, is freeze-dried, obtains gelatine microsphere, save.
It takes 0.1mg TGF protein dissolution in 10mlPBS step 5: being loaded into TGF albumen in gelatine microsphere, is then added
0.1g gelatine microsphere impregnates 36h, then 3000 revs/min of centrifuge washings are twice, is freeze-dried to get the gelatine microsphere containing albumen,
It saves.
Step 6: the gelatine microsphere containing albumen is loaded into the porous Titanium base of argentiferous, takes and contain TGF egg obtained by the 5th step
The protein liquid that white gelatine microsphere is dispersed in 3.5% is made into gelatine microsphere protein suspending liquid, ultrasonic 20min.Third step is made
Standby argentiferous POROUS TITANIUM basis material is placed in the gelatin solution that mass volume ratio is 3.5%, is taken out after immersion 45min and is transferred to again
It is taken out in aforementioned gelatine microsphere protein suspending liquid, after 36h and drying is to get argentiferous and the porous titanium composite material for carrying TGF microballoon.
Embodiment three
This example is a part of identical as example, and institute's difference is:
Step 1: the preparation of porous Titanium base, takes titanium valve and pore creating material ammonium hydrogen carbonate to mix according to 1:1 ratio,
Molding blank is placed in sintering furnace by compression moulding under 100MPa, rises to 180 DEG C by room temperature with the heating rate of 1 DEG C/min, heat preservation
5h removes ammonium hydrogen carbonate, forms porous structure；Then the sample after pre-burning is put into vacuum sintering furnace, with the liter of 5 DEG C/min
Warm rate is warming up to 1300 DEG C, keeps the temperature furnace cooling after 3h, and vacuum degree maintains 1.0 × 10-4Pa。
Step 2: the preparation of the multiple dimensioned porous Titanium base of pore structure, selecting the sulfuric acid of 0.1M is electrolyte, and voltage is
110V, reaction time 3min carry out the porous Titanium base material that anodic oxidation obtains having both macro hole and micropore to porous Titanium base
Material.
Step 3: growth in situ silver particles on POROUS TITANIUM basis material, porous Titanium base prepared by second step is immersed in
Concentration is the AgNO of 0.005M33h in solution, ultraviolet light 3h after taking-up are dried in vacuo to get growth in situ silver particles
POROUS TITANIUM basis material, for use.
Step 4: the preparation of gelatine microsphere,
(1) Arlacel-80 of the atoleine and 1.5ml that take 70ml mixes equal in the case where environment temperature is 60 DEG C of water bath conditions
It is even.1g gelatin powder is dissolved in deionized water at the same temperature.
(2) 60 DEG C are kept, gelatin solution is instilled in the mixed liquor of atoleine and Arlacel-80 and is emulsified, after 30min
Rapid cooling emulsion is added the glutaraldehyde that 4ml concentration is 25% when emulsion temperature is 4 DEG C and is crosslinked, the reaction time
For 1h.(3) after crosslinking is completed, the acetone that 30ml is added carries out water-oil separating, and time 1h finally uses acetone and anhydrous second
Alcohol replaces filtering and washing, and freeze-drying obtains gelatine microsphere, saves.
Step 5: gelatine microsphere, which is dispersed in 48h in the polypeptide protein liquid that concentration is 5%, is then added 0.1g gelatine microsphere
48h is impregnated, then 3500 revs/min of centrifuge washings are twice, freeze-drying saves to get the gelatine microsphere containing albumen.
Step 6: the gelatine microsphere containing albumen is loaded into the porous Titanium base of argentiferous, takes and contain polypeptide obtained by the 5th step
Gelatine microsphere be dispersed in 5% protein liquid and be made into gelatine microsphere protein suspending liquid, ultrasonic 20min.It will be prepared by third step
Argentiferous POROUS TITANIUM basis material is placed in the gelatin solution that mass volume ratio is 5%, is taken out after immersion 1h and is transferred to aforementioned gelatin again
It is taken out in microglobulin suspension, after 48h and drying is to get argentiferous and the porous titanium composite material for carrying polypeptide microballoon.
Example IV
This example and example one are essentially identical, and institute's difference is, gelatine microsphere is 0.1mg/ by impregnating the drug being loaded into
Ml phosphate.
Embodiment five
This example and example one are essentially identical, and institute's difference is: will be loaded with method of the gelatine microsphere of BMP-2 by being added dropwise
It instills argentiferous to carry on the POROUS TITANIUM basis material of TGF, then be dried in vacuo, taking-up sample, which continues to be added dropwise, after 30min is loaded with BMP-2
Gelatine microsphere.Dropwise addition-vacuum drying-dropwise addition-vacuum drying is repeated 5 times to get a kind of anti-to being loaded into porous Titanium base
The porous titanium composite material of microbial inoculum and the albumen of two kinds of different roles.
Porous titanium composite material obtained by this example, since its microballoon for carrying BMP-2 is covered on the microballoon for carrying TGF, space
The different of distribution realize that BMP-2 are first discharged in early stage, with BMP-2 release and carry BMP-2 gelatine microsphere diffusion,
TGF also gradually discharges in internal layer microballoon.It is realized with this and is discharged step by step, to respond the demand of tissue growth different phase.
Embodiment six
(1) porous Titanium base is prepared with the method for embodiment one and carry the gelatine microsphere of BMP-2, and will be loaded with BMP-2's
Gelatine microsphere is directly loaded into porous Titanium base.
(2) gelatine microsphere of preparation is immersed in the AgNO that concentration is 0.001M3Concentration, which is added, in solution, after 12h is
The NaBH of 0.004M4, after placing 12h, twice of filtering and washing is to get to carrying Gelatin microballoon, then will carry the dispersion of Gelatin microballoon
In deionized water.
(3) the load Gelatin microballoon prepared in (2) is loaded by the vacuum drying method of dropwise addition-vacuum drying-dropwise addition-
In porous Titanium base, it is repeated 5 times to get the porous titanium composite material with release function step by step is arrived.
Porous titanium composite material obtained by this example, release initial stage is Ag+It is first released from microballoon, with carrying, Gelatin is micro-
The diffusion of ball, the flowing of body fluid, the increase of gelatine microsphere and body fluid contact area, BMP-2 also gradually discharge.
Embodiment seven
This example is basically the same as the first embodiment, the difference is that: in the preparation of first step POROUS TITANIUM basis material
It selects the ratio of pore creating material (ammonium hydrogen carbonate) and titanium valve for 3:2 i.e. 60%, obtains porosity and the higher sample of percent opening.
Embodiment eight
This example is basically the same as the first embodiment, the difference is that: the sulfuric acid for selecting 0.1M is electrolyte, and voltage is
150V, reaction time 3min can be obtained the bigger multiple dimensioned POROUS TITANIUM basis material of micropore size.
The present invention prepare the porous titanium composite material of gained not only have the ability for promoting osteoblast and tissue growth but also
With long acting antibiotic ability.
Claims (3)
1. a kind of preparation method of porous titanium composite material, comprising the following steps:
Step 1: the preparation of porous Titanium base, takes titanium valve to mix with pore creating material ammonium hydrogen carbonate according to 1:1, pressure be 50~
Compression moulding under 100MPa；Molding blank is placed in pre-burning in sintering furnace, rises to 150~180 by room temperature with the rate of 1 DEG C/min
DEG C, 3~5h is kept the temperature, ammonium hydrogen carbonate is removed, forms the titanium sample of porous structure, the titanium sample after pre-burning is put into vacuum sintering furnace
Interior, vacuum degree maintains 10-3~10-4Pa is warming up to 1100 DEG C~1300 DEG C with the rate of 5 DEG C/min, keeps the temperature after 2~4h with furnace
It is cooling, up to porous Titanium base, take out spare；
Step 2: the preparation of the multiple dimensioned porous Titanium base of pore structure selects anodic oxidation reactions, to more using sulfuric acid as electrolyte
Hole Titanium base carries out anodic oxidation, forms 1~5 μm of micropore after oxidation reaction on hole wall, obtains macroscopic pores and passes through and micropore
The multiple dimensioned porous Titanium base of pore structure；
Step 3: growth in situ silver particles on porous Titanium base, it is molten to be immersed in silver nitrate for porous Titanium base prepared by second step
1~3h in liquid uses 1~3h of ultraviolet light after taking-up, vacuum drying obtains the porous Titanium base of growth in situ silver particles, to
With；
It is equal when environment temperature is 60 DEG C by atoleine and sorbester p17 in the ratio of 98:2 step 4: the preparation of gelatine microsphere
After even mixing, it is added dropwise in mutually synthermal aqueous gelatin solution and emulsifies cooling 30min；When aqueous gelatin solution is cooled to 4 DEG C
When, be added 4ml concentration be 5%~25% glutaraldehyde be crosslinked, the reaction time be 40min~1h, then be added acetone into
Row water-oil separation, is finally alternately washed on vacuum filtration machine using acetone and dehydrated alcohol, and it is micro- to obtain gelatin for freeze-drying
Ball saves；
Step 5: being loaded into albumen in gelatine microsphere, gelatine microsphere is dispersed in by the ratio for being 1:100 according to mass volume ratio
Concentration be 2%~5% protein liquid in 24~48h, after taking-up under conditions of 2500~3500r/min, centrifuge washing twice,
It is freeze-dried up to the gelatine microsphere of albumen is loaded into, saves；
Step 6: the gelatine microsphere containing albumen is loaded into the porous Titanium base of argentiferous, the bright of loading albumen obtained by the 5th step is taken
Glue microballoon is dispersed in ultrasound 20min in 2%~5% protein liquid and obtains the protein suspending liquid containing gelatine microsphere；Third step is made
The porous Titanium base of standby argentiferous is placed in the gelatin solution that mass volume ratio is 1~5%, is taken out after immersion 30min~1h and is turned again
Enter in foregoing proteins suspension, the POROUS TITANIUM composite wood for carrying protein microsphere to get argentiferous is taken out and spontaneously dried after 24~48h
Material.
2. a kind of preparation method of porous titanium composite material according to claim 1, which is characterized in that the anodic oxidation
The voltage of reaction is 90~110V, and sulfuric acid concentration is 0.01M~0.1M, and the time is 1~3min.
3. a kind of preparation method of porous titanium composite material according to claim 1, which is characterized in that the AgNO3Solution
Concentration is 0.001M~0.005M.
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| CN107824790A (en) * | 2017-10-25 | 2018-03-23 | 成都先进金属材料产业技术研究院有限公司 | A kind of preparation method of porous vanadium chromium titanium material |
| CN108144110A (en) * | 2017-12-12 | 2018-06-12 | 王建东 | A kind of preparation method of promoting healing type head injury titanium net composite material |
| CN108543109B (en) * | 2018-03-13 | 2020-09-18 | 淮阴工学院 | Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof |
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