CN110629228A - Surface treatment process of titanium nail for bone setting and titanium nail - Google Patents
Surface treatment process of titanium nail for bone setting and titanium nail Download PDFInfo
- Publication number
- CN110629228A CN110629228A CN201910990527.6A CN201910990527A CN110629228A CN 110629228 A CN110629228 A CN 110629228A CN 201910990527 A CN201910990527 A CN 201910990527A CN 110629228 A CN110629228 A CN 110629228A
- Authority
- CN
- China
- Prior art keywords
- titanium nail
- sample
- bone
- titanium
- surface treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000010936 titanium Substances 0.000 title claims abstract description 138
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 70
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 18
- 238000004381 surface treatment Methods 0.000 title claims abstract description 18
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims abstract description 25
- 229920002674 hyaluronan Polymers 0.000 claims abstract description 25
- 229960003160 hyaluronic acid Drugs 0.000 claims abstract description 25
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000005488 sandblasting Methods 0.000 claims abstract description 20
- 238000005530 etching Methods 0.000 claims abstract description 16
- 238000007788 roughening Methods 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005237 degreasing agent Methods 0.000 claims description 8
- 239000013527 degreasing agent Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 208000010392 Bone Fractures Diseases 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000009940 knitting Methods 0.000 claims 7
- 230000000694 effects Effects 0.000 abstract description 9
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000012792 lyophilization process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws or setting implements
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
- A61B17/86—Pins or screws or threaded wires; nuts therefor
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Veterinary Medicine (AREA)
- Neurology (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Molecular Biology (AREA)
- Medical Informatics (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Heart & Thoracic Surgery (AREA)
- Biomedical Technology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Materials For Medical Uses (AREA)
- Cosmetics (AREA)
Abstract
A surface treatment process of a titanium nail for bone setting and the titanium nail are provided, the surface of the titanium nail is roughened, the roughening treatment comprises one of sand blasting, acid etching, combination of sand blasting and acid etching, anodic oxidation, micro-arc oxidation or combination of anodic oxidation and micro-arc oxidation, so that a rough or porous structure is obtained on the surface, then residual liquid inside the rough or porous structure is removed in a freeze-drying mode, and hyaluronic acid is carried out in a vacuum filtration mode, so that the surface of the titanium nail has the specific capacity of inhibiting the adhesion growth of a bone surface, the titanium nail is prevented from having better compatibility with bone organisms, the easy nail taking effect is finally obtained, and the operation time and the pain of a patient are reduced.
Description
Technical Field
The invention relates to the field of medical instruments, in particular to a titanium nail for bone setting and a surface treatment process of the titanium nail.
Background
The titanium nail mentioned in the text is a fixing nail applied to medical instruments, and is matched with a bone fracture plate for use to realize the fixation of fracture and bone blocks, and the effect is obvious.
However, when the existing titanium-based material orthopedic implantation nail (i.e. titanium nail) is taken out after recovery, the titanium-based material has better biocompatibility, so that the nail is difficult to take out or cannot be taken out, great nail taking risk hidden danger is brought to an operator, and secondary pain is brought to the patient.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a surface treatment process of a titanium nail for bone setting, which removes biocompatibility between the titanium nail and a human body through the surface treatment of the titanium nail.
The technical scheme for solving the technical problem is as follows: a surface treatment process of an inert titanium nail for bone setting comprises the following steps:
1) soaking a titanium nail sample by using one or more of absolute ethyl alcohol, acetone or a metal surface degreasing agent, and then carrying out ultrasonic cleaning to remove stains on the surface of the sample;
2) roughening the surface of the titanium nail sample, wherein the roughening treatment comprises one of a sand blasting process, an acid etching process, a combination of the sand blasting process and the acid etching process, an anodic oxidation process, a micro-arc oxidation process or a combination of the anodic oxidation process and the micro-arc oxidation process, so that the surface of the titanium nail sample is in a porous structure;
3) carrying out freeze-drying treatment on the titanium nail sample subjected to the roughening treatment so as to remove residual liquid in a porous structure on the surface of the titanium nail sample;
4) and carrying out a vacuum suction filtration hyaluronic acid loading process on the surface of the titanium nail sample, so that the hyaluronic acid is attached in the porous structure.
Further, the sand blasting process comprises the following steps: selecting sand grains with the size of 40-100 meshes, continuously carrying out sand blasting on the surface of the titanium nail sample in the environment with the air pressure of 0.2-0.8 Mpa for 1-5 minutes, and then putting the titanium nail sample into pure water for cleaning and drying. The titanium nail surface porous structures with different sizes can be formed in the sand blasting process, and the size and the number of the titanium nail surface porous structures are in direct proportion to the size of the sand grain mesh number, the air pressure and the duration.
Further, the acid etching process comprises the following steps: and (3) putting the titanium nail sample into a solution containing sulfuric acid, hydrochloric acid and hydrofluoric acid for 5-30 minutes, and then putting the titanium nail sample into pure water for cleaning and drying. In the acid etching process, the size and the number of the porous structures on the surface of the titanium nail are in direct proportion to the time of putting the titanium nail into the solution.
Further, the anodic oxidation process comprises: and (3) putting the titanium nail sample into the anodic oxidation electrolyte, continuously oxidizing for 3-30 minutes under the voltage of 20-100V, and then putting the titanium nail sample into pure water for cleaning and drying. In the anodic oxidation process, the size and the number of the porous structures on the surface of the titanium nail are in direct proportion to the voltage and the continuous oxidation time of anodic oxidation.
Further, the micro-arc oxidation process comprises the following steps: placing the titanium nail sample into the electrolyte of micro-arc oxidation, wherein the cut-off voltage of the micro-arc oxidation power supply parameters is 360V-480V, and the current density is 0.05mA/cm2～0.7 mA/cm2The reaction time is 30-200S, and after the reaction is finished, the reaction product is put into pure water for cleaning and drying. In the micro-arc oxidation process, the size and the number of the porous structures on the surface of the titanium nail are in direct proportion to the cut-off voltage and the reaction time in the micro-arc oxidation and in inverse proportion to the current density.
Further, the lyophilization process comprises:
1) setting the temperature of a cold trap of a freeze dryer at-20 ℃ and carrying out continuous pre-cooling for 0.5-1 hour;
2) the titanium nail sample is put into a vacuum chamber of a freeze dryer for sealing and then is pumped, and meanwhile, the temperature of a cold trap of the freeze dryer is reduced to minus 40 ℃ to minus 50 ℃;
3) starting timing when the internal vacuum degree is 13-15 Pa after air extraction, and continuing for 1-10 hours;
4) and taking out the titanium nail sample after the end. Residual liquid in the porous structure can be effectively removed through a freeze-drying process, and the dryness and tidiness in the porous structure of the sample are guaranteed.
Preferably, the titanium nail sample is frozen for 12-24 hours at-18 to-80 ℃ before being placed in a vacuum chamber of a freeze dryer, so that the titanium nail sample has better drying property.
Further, the vacuum filtration hyaluronic acid loading process comprises the following steps:
1) preparing a hyaluronic acid solution;
2) soaking a part or the whole surface of the coated sample by using the prepared hyaluronic acid solution by one or more methods of dripping, spin coating and soaking;
3) placing the coated titanium nail sample in a vacuum chamber of a freeze dryer, a vacuum drying box or a suction filtration funnel for air suction;
4) when the air is pumped to the internal vacuum degree of 10-20 Pa, the timing is started and lasts for 0.2-10 hours. When the pressure and the duration time of the vacuum degree in the air exhaust are increased, the effect of attaching the hyaluronic acid on the porous structure is better.
5) After the air pumping is finished, emptying the vacuum chamber, the vacuum drying box or the suction filtering funnel of the freeze dryer to instantly increase the internal pressure to the atmospheric pressure;
6) the sample was removed.
The titanium nail for setting bones is prepared by the surface treatment process of each titanium nail for setting bones.
The invention has the beneficial effects that: the surface of the titanium nail is roughened, wherein the roughening treatment comprises one of sand blasting, acid etching, combination of sand blasting and acid etching, anodic oxidation, micro-arc oxidation or combination of anodic oxidation and micro-arc oxidation, so that a rough or porous structure is obtained on the surface, then residual liquid inside the rough or porous structure is removed in a freeze-drying mode, and hyaluronic acid is carried out in a vacuum filtration mode, so that the surface of the titanium nail has the specific capacity of inhibiting the adhesion growth of a bone surface, the titanium nail is removed and has better compatibility with bone organisms, the easy nail taking effect is finally obtained, and the operation time and the pain of a patient are reduced.
Drawings
None.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
A surface treatment process of a titanium nail for bone setting comprises the following steps:
example one
1) Soaking a titanium nail sample by using one or more of absolute ethyl alcohol, acetone or a metal surface degreasing agent, and then carrying out ultrasonic cleaning to remove stains on the surface of the sample;
2) selecting 40-mesh sand grains, continuously carrying out sand blasting on the surface of the titanium nail sample under the environment of 0.2Mpa for 2 minutes, and then putting the titanium nail sample into pure water for cleaning and drying.
3) Setting the temperature of a cold trap of a freeze dryer at-20 ℃ and carrying out precooling for 1 hour continuously;
4) the titanium nail sample is placed into a vacuum chamber of a freeze dryer for sealing and then is exhausted, and meanwhile, the temperature of a cold trap of the freeze dryer is reduced to-45 ℃;
5) starting timing when the internal vacuum degree is 14Pa after air suction, and continuing for 12 hours;
6) taking out the titanium nail sample after finishing;
7) preparing a hyaluronic acid solution;
8) soaking a part or the whole surface of the coated sample by using the prepared hyaluronic acid solution by one or more methods of dripping, spin coating and soaking;
9) placing the coated titanium nail sample in a vacuum chamber of a freeze dryer, a vacuum drying box or a suction filtration funnel for air suction;
10) the timing was started when the internal vacuum was evacuated to 15Pa for 12 hours.
11) After the air pumping is finished, emptying the vacuum chamber, the vacuum drying box or the suction filtering funnel of the freeze dryer to instantly increase the internal pressure to the atmospheric pressure;
12) the sample was removed.
Example two
In this example, the size of the sand grains in step 2) of the first example was selected to be 100 mesh, and the rest of the conditions were the same as those of the first example.
EXAMPLE III
In this example, the pressure in step 2) of the first example was selected to be 0.8MPa, and the rest of the conditions were the same as those in the first example.
According to the first, second and third comprehensive comparison embodiments, the larger the sand grain number is, and the larger the air pressure is, the more porous structures are produced on the surface of the titanium nail, and the larger the pore size of the pores is, so that the sand blasting process is very simple in operability and easy to realize, but the formed porous structures are uniform and inconsistent, so that the transparent acid attached to the surface is easy to fall off, and a very good nail taking effect cannot be achieved. The titanium nail prepared by the sand blasting process has a relatively large aperture on the surface, and is mainly applied to the situation that the size of the titanium nail is relatively large.
Example four
1) Soaking a titanium nail sample by using one or more of absolute ethyl alcohol, acetone or a metal surface degreasing agent, and then carrying out ultrasonic cleaning to remove stains on the surface of the sample;
2) and putting the titanium nail sample into a solution containing sulfuric acid, hydrochloric acid and hydrofluoric acid for 5 minutes, and after the titanium nail sample is put into pure water for cleaning and drying.
3) Setting the temperature of a cold trap of a freeze dryer at-20 ℃ and carrying out precooling for 1 hour continuously;
4) the titanium nail sample is placed into a vacuum chamber of a freeze dryer for sealing and then is exhausted, and meanwhile, the temperature of a cold trap of the freeze dryer is reduced to-45 ℃;
5) starting timing when the internal vacuum degree is 14Pa after air suction, and continuing for 12 hours;
6) taking out the titanium nail sample after finishing;
7) preparing a hyaluronic acid solution;
8) soaking a part or the whole surface of the coated sample by using the prepared hyaluronic acid solution by one or more methods of dripping, spin coating and soaking;
9) placing the coated titanium nail sample in a vacuum chamber of a freeze dryer, a vacuum drying box or a suction filtration funnel for air suction;
10) the timing was started when the internal vacuum was evacuated to 15Pa for 12 hours.
11) After the air pumping is finished, emptying the vacuum chamber, the vacuum drying box or the suction filtering funnel of the freeze dryer to instantly increase the internal pressure to the atmospheric pressure;
12) the sample was removed.
EXAMPLE five
In this example, the duration of step 2) of example four was extended to 30 minutes, and the remaining conditions were the same as in example four.
Comparing the fourth embodiment with the fifth embodiment, the longer the acid etching time is, the more the porous structures on the surface of the titanium nail are, but the titanium nail prepared by the acid etching process has uniform and inconsistent porous structures on the surface and relatively smaller porous structures, so that the effect of attaching the transparent acid on the surface of the titanium nail is relatively poor, and the excellent nail taking effect cannot be achieved.
EXAMPLE six
1) Soaking a titanium nail sample by using one or more of absolute ethyl alcohol, acetone or a metal surface degreasing agent, and then carrying out ultrasonic cleaning to remove stains on the surface of the sample;
2) selecting sand grains with the size of 50 meshes, continuously carrying out sand blasting on the surface of the titanium nail sample under the environment of 0.3Mpa for 2 minutes, and then putting the titanium nail sample into pure water for cleaning and drying.
3) And (3) putting the titanium nail sample into a solution containing sulfuric acid, hydrochloric acid and hydrofluoric acid for 10 minutes, and then putting the titanium nail sample into pure water for cleaning and drying.
4) Setting the temperature of a cold trap of a freeze dryer at-20 ℃ and carrying out precooling for 1 hour continuously;
5) the titanium nail sample is placed into a vacuum chamber of a freeze dryer for sealing and then is exhausted, and meanwhile, the temperature of a cold trap of the freeze dryer is reduced to-45 ℃;
6) starting timing when the internal vacuum degree is 14Pa after air suction, and continuing for 12 hours;
7) taking out the titanium nail sample after finishing;
8) preparing a hyaluronic acid solution;
9) soaking a part or the whole surface of the coated sample by using the prepared hyaluronic acid solution by one or more methods of dripping, spin coating and soaking;
10) placing the coated titanium nail sample in a vacuum chamber of a freeze dryer, a vacuum drying box or a suction filtration funnel for air suction;
11) the timing was started when the internal vacuum was evacuated to 15Pa for 12 hours.
12) After the air pumping is finished, emptying the vacuum chamber, the vacuum drying box or the suction filtering funnel of the freeze dryer to instantly increase the internal pressure to the atmospheric pressure;
13) the sample was removed.
By combining the first comparative example, the fourth comparative example and the sixth comparative example, compared with the sand blasting or the acid etching alone, the titanium nail obtained by combining the sand blasting process and the acid etching process has the advantages that the number of the porous structures on the surface of the titanium nail is relatively large, the porous structures are relatively uniform, but the sizes of the porous structures are relatively large and are not easy to control, and the titanium nail is relatively suitable for titanium nails with relatively large diameters.
EXAMPLE seven
1) Soaking a titanium nail sample by using one or more of absolute ethyl alcohol, acetone or a metal surface degreasing agent, and then carrying out ultrasonic cleaning to remove stains on the surface of the sample;
2) and putting the titanium nail sample into the anodic oxidation electrolyte, continuously oxidizing for 3 minutes under the voltage of 20V, and then putting the titanium nail sample into pure water for cleaning and drying.
3) Setting the temperature of a cold trap of a freeze dryer at-20 ℃ and carrying out precooling for 1 hour continuously;
4) the titanium nail sample is placed into a vacuum chamber of a freeze dryer for sealing and then is exhausted, and meanwhile, the temperature of a cold trap of the freeze dryer is reduced to-45 ℃;
5) starting timing when the internal vacuum degree is 14Pa after air suction, and continuing for 12 hours;
6) taking out the titanium nail sample after finishing;
7) preparing a hyaluronic acid solution;
8) soaking a part or the whole surface of the coated sample by using the prepared hyaluronic acid solution by one or more methods of dripping, spin coating and soaking;
9) placing the coated titanium nail sample in a vacuum chamber of a freeze dryer, a vacuum drying box or a suction filtration funnel for air suction;
10) the timing was started when the internal vacuum was evacuated to 15Pa for 12 hours.
11) After the air pumping is finished, emptying the vacuum chamber, the vacuum drying box or the suction filtering funnel of the freeze dryer to instantly increase the internal pressure to the atmospheric pressure;
12) the sample was removed.
Example eight
In this example, the voltage in step 2) of example seven was increased to 100V, and the remaining conditions were exactly the same as in example seven.
Example nine
In this example, the oxidation time in step 2) of example seven was increased to 30 minutes, with the remainder of the conditions being exactly the same as in example seven.
Combining the seven, eight and nine comparative examples, the larger the anodic oxidation voltage and the longer the oxidation time, the more and the larger the porous structure obtained, and the porous structure on the surface of the titanium nail obtained by anodic oxidation is relatively uniform, but the pore diameter of the porous structure is relatively smaller, so that the porous structure is suitable for the titanium nail with smaller diameter, and the test cost of anodic oxidation is higher.
Example ten
1) Soaking a titanium nail sample by using one or more of absolute ethyl alcohol, acetone or a metal surface degreasing agent, and then carrying out ultrasonic cleaning to remove stains on the surface of the sample;
2) placing the titanium nail sample into the micro-arc oxidation electrolyte, selecting the micro-arc oxidation power supply parameters with the cut-off voltage of 360V and the current density of 0.05mA/cm2And the reaction time is 30S, and after the reaction is finished, the reaction product is put into pure water for cleaning and drying.
3) Setting the temperature of a cold trap of a freeze dryer at-20 ℃ and carrying out precooling for 1 hour continuously;
4) the titanium nail sample is placed into a vacuum chamber of a freeze dryer for sealing and then is exhausted, and meanwhile, the temperature of a cold trap of the freeze dryer is reduced to-45 ℃;
5) starting timing when the internal vacuum degree is 14Pa after air suction, and continuing for 12 hours;
6) taking out the titanium nail sample after finishing;
7) preparing a hyaluronic acid solution;
8) soaking a part or the whole surface of the coated sample by using the prepared hyaluronic acid solution by one or more methods of dripping, spin coating and soaking;
9) placing the coated titanium nail sample in a vacuum chamber of a freeze dryer, a vacuum drying box or a suction filtration funnel for air suction;
10) the timing was started when the internal vacuum was evacuated to 15Pa for 12 hours.
11) After the air pumping is finished, emptying the vacuum chamber, the vacuum drying box or the suction filtering funnel of the freeze dryer to instantly increase the internal pressure to the atmospheric pressure;
12) the sample was removed.
EXAMPLE eleven
In this example, the off-voltage in step 2) of example ten was increased to 480V, and the remaining conditions were exactly the same as in example ten.
In example twelve, the current density in step 2) of example ten was increased to 0.7mA/cm2The rest of the conditions were exactly the same as in example ten.
In example thirteen, the reaction time in step 2) of example ten was increased to 200S, and the remaining conditions were exactly the same as in example ten.
Compared with the tenth, eleventh, twelfth and thirteenth embodiments, the relatively high cut-off voltage, the relatively small current density and the relatively long reaction time can make the porous structure on the surface of the titanium nail more uniform and fine, and the porous structures with different sizes can be obtained through the different parameter settings of the three conditions, so that the requirements of different sizes of the titanium nail can be met, and the whole process of the micro-arc oxidation process is relatively simple and easy to control.
Example fourteen
1) Soaking a titanium nail sample by using one or more of absolute ethyl alcohol, acetone or a metal surface degreasing agent, and then carrying out ultrasonic cleaning to remove stains on the surface of the sample;
2) and putting the titanium nail sample into the anodic oxidation electrolyte, continuously oxidizing for 5 minutes under the voltage of 20V, and then putting the titanium nail sample into pure water for cleaning and drying.
3) Placing the titanium nail sample into the micro-arc oxidation electrolyte, selecting the micro-arc oxidation power supply parameters with the cut-off voltage of 360V and the current density of 0.1mA/cm2And the reaction time is 30S, and after the reaction is finished, the reaction product is put into pure water for cleaning and drying.
4) Setting the temperature of a cold trap of a freeze dryer at-20 ℃ and carrying out precooling for 1 hour continuously;
5) the titanium nail sample is placed into a vacuum chamber of a freeze dryer for sealing and then is exhausted, and meanwhile, the temperature of a cold trap of the freeze dryer is reduced to-45 ℃;
6) starting timing when the internal vacuum degree is 14Pa after air suction, and continuing for 12 hours;
7) taking out the titanium nail sample after finishing;
8) preparing a hyaluronic acid solution;
9) soaking a part or the whole surface of the coated sample by using the prepared hyaluronic acid solution by one or more methods of dripping, spin coating and soaking;
10) placing the coated titanium nail sample in a vacuum chamber of a freeze dryer, a vacuum drying box or a suction filtration funnel for air suction;
11) the timing was started when the internal vacuum was evacuated to 15Pa for 12 hours.
12) After the air pumping is finished, emptying the vacuum chamber, the vacuum drying box or the suction filtering funnel of the freeze dryer to instantly increase the internal pressure to the atmospheric pressure;
13) the sample was removed.
By combining the seventh embodiment, the tenth embodiment and the fourteenth embodiment, although the porous structure of the surface of the titanium nail obtained by combining the anodic oxidation and the micro-arc oxidation is fine and uniform and the size of the porous structure can be adjusted, the porous structure has no advantage compared with a single micro-arc oxidation process, and the whole process is complicated and the production cost is increased.
According to the first to the fourteenth embodiments, the porous structure obtained by directly performing one or two combined actions of the sand blasting process and the acid etching process is rough and uniform, so that the uniformity of adhesion is inconsistent, and the biocompatibility between the titanium nail and a human body is affected. The titanium nail directly passes through the micro-arc oxidation process, the depth of the porous structure on the surface of the titanium nail can be adjusted to be moderate through parameters, the uniformity is good, the transparent acid can be attached to the porous structure for a long time, the using effect is good, the separation phenomenon can not occur after the titanium nail is used for a long time, the biocompatibility between a human body and the titanium nail is well eliminated, and the excellent nail taking effect is finally achieved.
The titanium nail for bone setting prepared by the embodiments can well meet the fixation of fracture and bone block in the medical field, when the separation is needed, the titanium nail and the human body are driven out in a biocompatible way due to the transparent acid in the titanium nail, so that the situation that the nail is difficult to take out or cannot be taken out is avoided when the nail is taken out, and the pain of taking the nail for a patient is avoided.
The above embodiment is only one of the preferable embodiments of the present patent, and any changes made without departing from the scope of the present patent are within the scope of the present patent.
Claims (9)
1. A surface treatment process of a titanium nail for bone setting is characterized by comprising the following steps:
1) soaking a titanium nail sample by using one or more of absolute ethyl alcohol, acetone or a metal surface degreasing agent, and then carrying out ultrasonic cleaning to remove stains on the surface of the sample;
2) roughening the surface of the titanium nail sample, wherein the roughening treatment comprises one of a sand blasting process, an acid etching process, a combination of the sand blasting process and the acid etching process, an anodic oxidation process, a micro-arc oxidation process or a combination of the anodic oxidation process and the micro-arc oxidation process, so that the surface of the titanium nail sample is in a porous structure;
3) carrying out freeze-drying treatment on the titanium nail sample subjected to the roughening treatment so as to remove residual liquid in a porous structure on the surface of the titanium nail sample;
4) and carrying out a vacuum suction filtration hyaluronic acid loading process on the surface of the titanium nail sample, so that the hyaluronic acid is attached in the porous structure.
2. The surface treatment process of the bone-knitting titanium nail according to claim 1, characterized in that: the sand blasting process comprises the following steps: selecting sand grains with the size of 40-100 meshes, continuously carrying out sand blasting on the surface of the titanium nail sample in the environment with the air pressure of 0.2-0.8 Mpa for 1-5 minutes, and then putting the titanium nail sample into pure water for cleaning and drying.
3. The surface treatment process of the bone-knitting titanium nail according to claim 1, characterized in that: the acid etching process comprises the following steps: and (3) putting the titanium nail sample into a solution containing sulfuric acid, hydrochloric acid and hydrofluoric acid for 5-30 minutes, and then putting the titanium nail sample into pure water for cleaning and drying.
4. The surface treatment process of the bone-knitting titanium nail according to claim 1, characterized in that: the anodic oxidation process comprises the following steps: and (3) putting the titanium nail sample into the anodic oxidation electrolyte, continuously oxidizing for 3-30 minutes under the voltage of 20-100V, and then putting the titanium nail sample into pure water for cleaning and drying.
5. The surface treatment process of the bone-knitting titanium nail according to claim 1, characterized in that: the micro-arc oxidation process comprises the following steps: placing the titanium nail sample into the electrolyte of micro-arc oxidation, wherein the cut-off voltage of the micro-arc oxidation power supply parameters is 360V-480V, and the current density is 0.05mA/cm2～0.7 mA/cm2The reaction time is 30-200S, and after the reaction is finished, the reaction product is put into pure water for cleaning and drying.
6. The surface treatment process of the bone-knitting titanium nail according to claim 1, characterized in that: the freeze-drying treatment comprises the following steps:
1) setting the temperature of a cold trap of a freeze dryer at-20 ℃ and carrying out continuous pre-cooling for 0.5-1 hour;
2) the titanium nail sample is put into a vacuum chamber of a freeze dryer for sealing and then is pumped, and meanwhile, the temperature of a cold trap of the freeze dryer is reduced to minus 40 ℃ to minus 50 ℃;
3) starting timing when the internal vacuum degree is 13-15 Pa after air extraction, and continuing for 1-10 hours;
4) and taking out the titanium nail sample after the end.
7. The surface treatment process of the bone-knitting titanium nail according to claim 6, characterized in that: the titanium nail sample is frozen for 12-24 hours at-18 to-80 ℃ before being placed in a vacuum chamber of a freeze dryer.
8. The surface treatment process of the bone-knitting titanium nail according to any one of claims 1 to 7, characterized in that: the vacuum filtration hyaluronic acid loading process comprises the following steps:
1) preparing a hyaluronic acid solution;
2) soaking a part or the whole surface of the coated sample by using the prepared hyaluronic acid solution by one or more methods of dripping, spin coating and soaking;
3) placing the coated titanium nail sample in a vacuum chamber of a freeze dryer, a vacuum drying box or a suction filtration funnel for air suction;
4) starting timing when the air is pumped until the internal vacuum degree is 10-20 Pa, and continuing for 0.2-10 hours;
5) after the air pumping is finished, emptying the vacuum chamber, the vacuum drying box or the suction filtering funnel of the freeze dryer to instantly increase the internal pressure to the atmospheric pressure;
6) the sample was removed.
9. A titanium nail for setting a bone is characterized in that: the titanium nail is processed by the surface treatment process of the titanium nail for bone fracture according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910990527.6A CN110629228B (en) | 2019-10-18 | 2019-10-18 | Surface treatment process of titanium nail for bone setting and titanium nail |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910990527.6A CN110629228B (en) | 2019-10-18 | 2019-10-18 | Surface treatment process of titanium nail for bone setting and titanium nail |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110629228A true CN110629228A (en) | 2019-12-31 |
| CN110629228B CN110629228B (en) | 2020-10-23 |
Family
ID=68976678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910990527.6A Active CN110629228B (en) | 2019-10-18 | 2019-10-18 | Surface treatment process of titanium nail for bone setting and titanium nail |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110629228B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173824A (en) * | 1995-02-07 | 1998-02-18 | 菲迪亚高级生物多聚合物有限公司 | Process for the coating of objects with hyaluronic acid, derivatives thereof, and natural and semisynthetic polymers |
| US20110262518A1 (en) * | 2010-04-27 | 2011-10-27 | Smyth Stuart K J | Treatment for cardiac injuries created by myocardial infarction |
| CN102579145A (en) * | 2012-02-23 | 2012-07-18 | 中国人民解放军第四军医大学 | Dental implant and preparation method thereof |
| CN103656750A (en) * | 2013-12-07 | 2014-03-26 | 西南交通大学 | Method for improving various bionic functions on surface of cardiovascular implant material |
| CN108310471A (en) * | 2018-01-04 | 2018-07-24 | 重庆大学 | A kind of good enzyme response antibacterial titanium preparation method of biocompatibility |
-
2019
- 2019-10-18 CN CN201910990527.6A patent/CN110629228B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173824A (en) * | 1995-02-07 | 1998-02-18 | 菲迪亚高级生物多聚合物有限公司 | Process for the coating of objects with hyaluronic acid, derivatives thereof, and natural and semisynthetic polymers |
| US20110262518A1 (en) * | 2010-04-27 | 2011-10-27 | Smyth Stuart K J | Treatment for cardiac injuries created by myocardial infarction |
| CN102579145A (en) * | 2012-02-23 | 2012-07-18 | 中国人民解放军第四军医大学 | Dental implant and preparation method thereof |
| CN103656750A (en) * | 2013-12-07 | 2014-03-26 | 西南交通大学 | Method for improving various bionic functions on surface of cardiovascular implant material |
| CN108310471A (en) * | 2018-01-04 | 2018-07-24 | 重庆大学 | A kind of good enzyme response antibacterial titanium preparation method of biocompatibility |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110629228B (en) | 2020-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5104410A (en) | Surgical implant having multiple layers of sintered porous coating and method | |
| EP1273312B1 (en) | Implant for cartilage tissue regeneration | |
| CN102579145B (en) | Dental implant and preparation method thereof | |
| EP2967835B1 (en) | Soft tissue repair allografts and methods for preparing same | |
| US7879092B2 (en) | Dental implant coated with recombinant bone morphogenic protein | |
| CN110629228B (en) | Surface treatment process of titanium nail for bone setting and titanium nail | |
| CN103361702A (en) | Method for surface modification of dental implant | |
| CN108004527A (en) | A kind of preparation method of zinc doping hydroxyapatite coating layer for magnesium alloy materials | |
| CN107281535B (en) | Giant salamander secretion viscous biomembrane and preparation method and application thereof | |
| CN101049516A (en) | Imbedded body in porous titanium of biologic medical use, and preparation method | |
| CN102861358A (en) | Method for manufacturing novel biological cartilage support by using umbilical cord Wharton jelly | |
| CN105624762B (en) | Method for preparing bioactive composite coating on surface of titanium or titanium alloy | |
| CN110420354B (en) | Enhanced silk fibroin artificial jaw carrier bracket and preparation method thereof | |
| CN102921034A (en) | Composite dressing of pig accellular dermal matrix and preparation method of composite dressing | |
| CN114855024A (en) | Porous tantalum medical implant material and preparation method and application thereof | |
| CN112301399A (en) | Surface treatment method for dental implant | |
| CN112174677B (en) | Preparation method of silicon nitride trabecula bone | |
| CN119140397A (en) | Freeze-drying treatment process suitable for bioactive coating | |
| CN109701077B (en) | Micropore regeneration tissue matrix and preparation and application thereof | |
| CN101766538B (en) | Rare earth element cerium slow-release artificial tooth root based on nanotube array surface | |
| CN105709276B (en) | A kind of chorion de-cell liquid and method for removing cells | |
| EP4176907A1 (en) | Skin graft supplementing/cushioning member for auricle skin defect | |
| CN111588506B (en) | Application of vitamin C-containing titanium implant storage solution | |
| KR101797465B1 (en) | Alginate foam with improved physical properties and manufacturing method thereof | |
| CN115634323B (en) | Method for sealing holes of medical magnesium material micro-arc oxidation bioprotein |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |