CN117139642B - Powder removal method for manufacturing medical porous titanium alloy by additive and application of powder removal method - Google Patents
Powder removal method for manufacturing medical porous titanium alloy by additive and application of powder removal method Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 81
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- 230000000996 additive effect Effects 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
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- 239000000243 solution Substances 0.000 claims description 23
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 13
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/62—Treatment of workpieces or articles after build-up by chemical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a powder removing method for medical porous titanium alloy for additive manufacturing and application thereof, and relates to the technical fields of additive manufacturing post-treatment technology and 3D printing medical treatment. A powder removal method for additively manufacturing a medical porous titanium alloy, comprising the following steps: firstly, soaking medical porous titanium alloy in an acid etching solution, and taking out; then cleaning the treated medical porous titanium alloy by adopting ultrasonic waves; soaking the treated medical porous titanium alloy in the acidic etching solution again, taking out, cleaning again by adopting ultrasonic waves, and repeating the steps to keep the total etching time to be 2-20min. The method of combining graded chemical etching with ultrasonic cleaning can rapidly and thoroughly remove most of sticky powder in the medical porous titanium alloy on the premise of not reducing the mechanical property of the formed part, and solves the problem that the powder removing effect and the mechanical property requirement cannot be simultaneously met at present.
Description
Technical Field
The invention relates to the technical fields of additive manufacturing post-treatment technology and 3D printing medical treatment, in particular to a powder removing method of medical porous titanium alloy for additive manufacturing and application thereof.
Background
Laser powder bed fusion (laser powder bed fusion, LPBF) is a method that is more used in rapid prototyping technology and is a very promising metal additive manufacturing technology. As the aging population increases, the incidence of osteoporosis, arthritis, and other musculoskeletal diseases also increases greatly. Therefore, the additive manufacturing technology is applied and researched not only in the fields of automobiles, aerospace, ocean engineering and the like, but also in the medical field, and the influence of the additive manufacturing technology is larger and larger. In the past, orthopedic implants used clinically often had only a fixed gauge, which resulted in implants on the market that were not fully suitable for every patient. But now, the additive manufacturing technology can be utilized to customize implants with different specifications and sizes according to different situations of patients, and the development of the additive manufacturing technology is promoted while bringing good news to the patients.
A large number of materials for medical additive manufacturing are used nowadays, typically metallic materials, of which most are titanium alloys, and some are cobalt-chromium alloys, stainless steel alloys, etc. The titanium alloy has the characteristics of high strength, low density, low temperature resistance, corrosion resistance, no magnetism and the like. The 3D printing orthopaedics implant made of the titanium alloy not only meets the requirements of high strength, porosity and light weight, but also has excellent biocompatibility and can well promote the growth and regeneration of bones in the implant. But the hardness and rigidity of the metal material are far greater than those of human bones, and the stress shielding effect is easy to be induced when the metal material is implanted into a human body, so that the rigidity of the bone implant is adjusted by adopting a porous structure, and the bone implant is beneficial to the growth of tissues around the bone implant.
Because of the complexity of the porous structure and the influence of factors such as different quick melting degrees of titanium alloy powder in high temperature and sedimentation of a molten pool in the laser powder bed fusion forming process, compared with a common solid structure, the porous structure is more prone to the conditions that powder is not thoroughly fused or powder is attached to a product structure after printing is finished. Many specialists have found that there is a lot of powder adhering inside the porous structure of the titanium alloy formed by additive manufacturing, and if the product implanted into the human body contains these residual powders, the residual powders may fall off and flow with blood over time, causing safety hazards such as inflammation, and thus introducing new biological risks. There are also many specialists who use different techniques for removing powder from porous structures. However, the powder removing effect is not ideal, and the mechanical properties are seriously affected. As in the patent of publication No. CN112387984a, a specific design is made on a post-treatment device for powder sticking in a porous structure for additive manufacturing, although the device is used for better removing residual powder in the porous structure for 3D printing, the powder sticking removing process is needed to be completed with the aid of an experimental device, a certain technical and reproduction difficulty exists, simplicity and operability are not possessed, and the performance of the structure after the residual powder removing is not mentioned, for example, paper Surface Modification of Ti Al4V Open Porous Structures Produced by Additive Manufacturing from Grzegorz in belgium is used for soaking the porous titanium alloy structure for additive manufacturing for 10 minutes, and the result is that although the surface roughness is greatly reduced, most of the powder sticking is removed, the mechanical performance is reduced by about 50%, the rod diameter is reduced by about 22%, and a certain limitation exists, so that the requirements of bone implant can not be met in two aspects at the same time.
Therefore, how to remove insoluble particle residues in the porous structure of the titanium alloy orthopedic implant device for additive manufacturing without additional devices, and fully ensure the mechanical properties of the structure at the same time becomes one of the key problems of research, and is a problem which each research and development production enterprise and scientific research institution must face.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a powder removing method for manufacturing medical porous titanium alloy by additive and application thereof. The invention adopts a method of combining graded chemical etching with ultrasonic cleaning, can rapidly and thoroughly remove most of sticky powder in medical porous titanium alloy on the premise of not reducing the mechanical property of a formed part, solves the problem that the prior art can not simultaneously meet the requirements of the powder removing effect and the mechanical property, further ensures the application of additive manufacturing technology in the medical field, and achieves the aim of improving the mechanical property through an effective sticky powder removing method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a powder removal method for additively manufactured medical porous titanium alloys, comprising the steps of:
(1) Soaking medical porous titanium alloy in an acidic etching solution for 1-8min, and then taking out, wherein the acidic etching solution is a mixed solution of hydrofluoric acid, nitric acid and water, the concentration of the hydrofluoric acid is 35-45%, the concentration of the nitric acid is 55-65%, and the volume ratio of the hydrofluoric acid to the nitric acid to the water is (2-13): (2-13): 50;
(2) Cleaning the medical porous titanium alloy treated in the step (1) by adopting ultrasonic waves;
(3) Soaking the medical porous titanium alloy subjected to ultrasonic cleaning in the step (2) in the acid etching solution in the step (1) again for 1-8min, taking out, and cleaning again by adopting ultrasonic waves; repeating the step (1) and the step (2) until the total etching time is 2-20min;
(4) And (3) drying the medical porous titanium alloy treated in the step (3), and taking out for later use.
The invention adopts a method of combining graded chemical etching with ultrasonic cleaning, and reduces the problem of mechanical property reduction caused by direct long-time soaking in acid etching solution.
In the invention, if the total etching time is less than 2min, the effect of removing the adhesion powder in the medical porous titanium alloy is poor, and if the total etching time exceeds 20min, the phenomenon that the rod diameter structure is damaged is obviously generated. The total etching time is controlled within the range limited by the invention, so that the adhering powder in the medical porous titanium alloy can be removed completely, and the mechanical property of the medical porous titanium alloy is ensured not to be reduced. If the concentration of hydrofluoric acid and nitric acid is too high, the situation of over etching can occur, so that the mechanical properties of the medical porous titanium alloy can be greatly influenced. Therefore, the method can balance the influence of the adhesive powder removal effect and the mechanical property in the medical porous titanium alloy by controlling the concentration of hydrofluoric acid and nitric acid and the total etching time within a specific range.
Preferably, in the step (1), the concentration of hydrofluoric acid is 45%, the concentration of nitric acid is 55%, and the volume ratio of hydrofluoric acid to nitric acid is 2: (5-13).
More preferably, in the step (1), the volume ratio of hydrofluoric acid to nitric acid is 2:12.
The acidic etching solution selects the hydrofluoric acid and the nitric acid with the specific concentration and the specific volume, so that the removal effect of the adhesive powder in the medical porous titanium alloy is improved, and the mechanical property of the medical porous titanium alloy is further improved.
Preferably, the etching time in the step (1) and the step (3) may be 1,2, 4, 8min, or any other value in 1-8 min.
More preferably, the etching time in each of the step (1) and the step (3) is 1min.
Preferably, the total etching time in the step (3) is 16min.
The specific graded etching time and total etching time are adopted in the invention, so that the powder adhered on the rod diameter can be uniformly removed, and the mechanical property of the medical porous titanium alloy can be improved.
Preferably, the power of the ultrasonic wave in the step (2) is 100-2000W, and the frequency of the ultrasonic wave is 20-130kHz.
In the invention, the ultrasonic wave adopts the power and the frequency in the range, so that suspended particles in the solution can be better removed, resources are saved, and the structure of the rod diameter is not easy to damage. Therefore, the power and the frequency of the ultrasonic wave are limited within the scope of the invention, so that the powder particles which are dropped but blocked in the medical porous titanium alloy can be cleaned in time, most of the adhered powder particles on the surface and the side surface of the rod can be removed better, and the mechanical property of the rod can be further improved.
Preferably, the power of the ultrasonic wave in the step (2) may be 100W, 200W, 500W, 800W, 1000W, 1200W, 1500W, 1800W, 2000W, or any other value in the range of 100-2000W.
Preferably, the ultrasonic wave in the step (2) has a frequency of 20-80kHz, and the workpiece with the complex surface shape or the holes is cleaned.
Preferably, the ultrasonic wave in the step (2) has a frequency of 80-130kHz, and the computer and the microelectronic element are cleaned.
Preferably, the power of the ultrasonic wave in the step (2) is 100-120W, and the frequency of the ultrasonic wave is 40-80kHz.
Preferably, the preparation method of the medical porous titanium alloy comprises the following steps:
(1) Adding titanium alloy powder into laser powder bed melting equipment, and opening an argon valve to ensure that the oxygen concentration in a working chamber is lower than 200ppm;
(2) After a model drawn by the three-dimensional modeling software is imported into an equipment computer, the process parameters of the laser melting technology are set as follows: the laser power is 30-400W, the exposure time is 5-300 mu s, the point spacing is 5-400 mu m, the layer thickness is 20-100 mu m, and the laser beam is utilized to scan the melted powder layer by layer, so as to prepare the medical porous titanium alloy molding.
When the medical porous titanium alloy is prepared, the laser powder bed melting equipment converts information in a three-dimensional model into a plurality of slices, each slice is limited to be a cross-section layer of the part, laser beams are utilized to scan melted powder layer by layer, a formed part of the medical porous titanium alloy is obtained, and the formed part is separated from a platform plate of an SLM machine through an electric spark machining (discharge machining) linear cutting process on the CMNE machine.
Preferably, the laser power in the step (2) is 250W, the exposure time is 50 mu s, the dot spacing is 50 mu m, the line spacing is 0.07mm, and the layer thickness is 50 mu m.
Preferably, the titanium alloy powder in the step (1) comprises the following components in percentage by mass:
5.5-6.5% of Al; v3.5-4.5%; fe 0.25%; c0.08%; n0.03%; h0.01%; o0.13%; the balance being Ti.
In a second aspect, the invention provides an application of the medical porous titanium alloy treated by the method in orthopedic implants in the medical field.
The medical porous titanium alloy treated by the sticky powder removing method is applied to orthopedic implants, and can fully meet the requirements of the orthopedic implants in the medical field.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method solves the problem that the traditional post-treatment methods such as sand blasting, micro abrasive gas jet and the like are difficult to enter the porous structure, and the problems of abrasive residue and hard particle damage structure are avoided, so that the requirements of orthopedic implants in the medical field are fully met.
(2) The method combining graded chemical etching with ultrasonic cleaning is beneficial to reducing the problems of mechanical property reduction and the like caused by direct long-time soaking in an acidic solution.
(3) The method provided by the invention can effectively remove the powder adhered on the rod diameter uniformly by combining the graded chemical etching with ultrasonic cleaning through the titanium alloy porous structure formed by melting the laser powder bed, and simultaneously improves the compressive strength and the elastic modulus of the structure, thereby realizing the personalized customization preparation of the orthopedic implant.
Drawings
FIG. 1 is a graph of the micro-morphology of a titanium alloy powder in accordance with the present invention.
FIG. 2 is a schematic diagram of a porous titanium alloy structural shaped member prepared by a laser powder bed melting technique in the present invention.
Fig. 3 is an SEM image of a support rod directly soaked in solutions of different proportions according to the present invention, (a) 2:5, (b) 2:9, (c) 2:13, (d) 2:17.
FIG. 4 shows the macroscopic morphology (a, b) of LPBF formed porous structures under an optical microscope in accordance with the present invention; SEM photographs (d, e) of the support bar (c) and the bar junction at different positions.
FIG. 5 is a macro-morphology (a, b) of the porous structure observed by an optical microscope in comparative example 6 of the present invention; SEM micrograph of the support bar (c, d) and bar junction (f) of example 4; SEM micrograph of the support bar (e) in comparative example 8.
FIG. 6 is a graphical representation of stress-strain average curves for uniaxial compression experiments in accordance with the present invention.
Detailed Description
For better illustrating the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples, but the scope and embodiments of the present invention are not limited thereto.
Materials, reagents and the like used in the following examples are commercially available ones unless otherwise specified.
Preparation example
The preparation method of the medical porous titanium alloy comprises the following steps:
(1) Adding titanium alloy powder into laser powder bed melting equipment, wherein the microscopic morphology of the titanium alloy powder is shown in figure 1, and opening an argon valve to ensure that the oxygen concentration in a working chamber is lower than 200ppm; the model of the laser powder bed melting equipment was RENISHAW AM400,400, london, UK, nd: the YAG laser has the wavelength of 1075nm, the diameter of the laser beam of 70 mu m, and the effective forming area range of 250mm multiplied by 300mm; the working gas in the melting chamber of the laser powder bed is argon, and the purity is 99.999 vol%;
(2) After a model drawn by the three-dimensional modeling software is imported into an equipment computer, the process parameters of the laser melting technology are set as follows: the apparatus formed a molded sample of the medical porous titanium alloy as shown in fig. 2 by converting the information in the three-dimensional model into a plurality of slices, each slice being defined as a cross-sectional layer of the part, using a laser beam scanning the melted powder layer by layer, forming a sample of the medical porous titanium alloy as shown in fig. 2, and separating the sample from the platen of the SLM machine by an electric discharge machining (electro discharge machining) wire cutting process on a CMNE machine, with a laser power of 250W, an exposure time of 50 mus, a spot pitch of 50 μm, and a wire pitch of 0.07mm, and a layer thickness of 50 μm.
Wherein, the diameter of the medical porous titanium alloy is 0.6mm, the cell size is 4mm, and the rod inclination angle is about 45 degrees. The BCC type body-centered cubic porous structure is obtained by modeling by the solidworks software, and is imported into a computer of laser powder bed melting equipment after being exported in STL format, or special modeling software such as UG, pro/E, CATIA and the like can be selected.
The titanium alloy powder is TC4 titanium alloy powder (prepared by a gas atomization method, feikang rapid manufacturing technology Co., ltd., tin-free, china), the diameter of TC4 titanium alloy powder particles is 15-53 mu m, and the titanium alloy powder comprises the following components in percentage by mass: 5.5% of Al; v3.5%; fe 0.25%; c0.08%; n0.03%; h0.01%; o0.13%; 90.5% of Ti.
Example 1
The embodiment discloses a powder removal method for manufacturing medical porous titanium alloy by additive, which comprises the following steps:
(1) Soaking medical porous titanium alloy in an acidic etching solution, wherein the acidic etching solution is a mixed solution of hydrofluoric acid, nitric acid and water, the etching time is 1min, and then taking out, wherein the concentration of the hydrofluoric acid is 45%, the concentration of the nitric acid is 55%, and the volume ratio of the hydrofluoric acid to the nitric acid to the water is 2:13:50;
(2) Cleaning the medical porous titanium alloy treated in the step (1) by adopting ultrasonic waves, wherein the power of the ultrasonic waves is 120W, and the frequency of the ultrasonic waves is 40kHz;
(3) Soaking the medical porous titanium alloy subjected to ultrasonic cleaning in the step (2) in the mixed solution of hydrofluoric acid, nitric acid and water in the step (1) again, wherein the etching time is 1min, taking out, cleaning by adopting an ultrasonic cleaner again, wherein the power of the ultrasonic cleaner is 120W, the frequency is 40kHz, the size of an inner groove is 240mm multiplied by 140mm multiplied by 100mm, the temperature is 25 ℃, taking out after ultrasonic cleaning for 3min, and then repeating the step (1) and the step (2), and keeping the total etching time to be 2min;
(4) And (3) drying the medical porous titanium alloy treated in the step (3) by a vacuum drying oven, and taking out for later use.
Example 2
The embodiment discloses a powder removal method for manufacturing medical porous titanium alloy by additive, which comprises the following steps:
(1) Soaking medical porous titanium alloy in an acidic etching solution, wherein the acidic etching solution is a mixed solution of hydrofluoric acid, nitric acid and water, the etching time is 1min, and then taking out, wherein the concentration of the hydrofluoric acid is 35%, the concentration of the nitric acid is 65%, and the volume ratio of the hydrofluoric acid to the nitric acid to the water is 13:2:50;
(2) Cleaning the medical porous titanium alloy treated in the step (1) by adopting ultrasonic waves, wherein the power of the ultrasonic waves is 120W, and the frequency of the ultrasonic waves is 40kHz;
(3) Soaking the medical porous titanium alloy subjected to ultrasonic cleaning in the step (2) in the mixed solution of hydrofluoric acid, nitric acid and water in the step (1) again, wherein the etching time is 8min, taking out, cleaning by adopting an ultrasonic cleaner again, wherein the power of the ultrasonic cleaner is 120W, the frequency is 40kHz, the size of an inner groove is 240mm multiplied by 140mm multiplied by 100mm, the temperature is 25 ℃, taking out after ultrasonic cleaning for 3min, and then repeating the step (1) and the step (2), and keeping the total etching time to be 20min;
(4) And (3) drying the medical porous titanium alloy treated in the step (3) by a vacuum drying oven, and taking out for later use.
Example 3
The embodiment discloses a powder removal method for manufacturing medical porous titanium alloy by additive, which comprises the following steps:
(1) Soaking medical porous titanium alloy in an acidic etching solution, wherein the acidic etching solution is a mixed solution of hydrofluoric acid, nitric acid and water, the etching time is 1min, and then taking out, wherein the concentration of the hydrofluoric acid is 45%, the concentration of the nitric acid is 55%, and the volume ratio of the hydrofluoric acid to the nitric acid to the water is 2:5:50;
(2) Cleaning the medical porous titanium alloy treated in the step (1) by adopting ultrasonic waves, wherein the power of the ultrasonic waves is 130W, and the frequency of the ultrasonic waves is 20kHz;
(3) Soaking the medical porous titanium alloy subjected to ultrasonic cleaning in the step (2) in the mixed solution of hydrofluoric acid, nitric acid and water in the step (1) again, wherein the etching time is 1min, taking out, cleaning by adopting an ultrasonic cleaner again, wherein the frequency of the ultrasonic cleaner is 20kHz, the power is 130W, the size of an inner groove is 240mm multiplied by 140mm multiplied by 100mm, the temperature is 25 ℃, taking out after ultrasonic cleaning for 3min, and repeating the step (1) and the step (2) for 16 times, and keeping the total etching time to be 16min;
(4) And (3) drying the medical porous titanium alloy treated in the step (3) by a vacuum drying oven, and taking out for later use.
Example 4
The difference from example 3 is that the volume ratio of hydrofluoric acid and nitric acid in step (1) is 2:12, the other steps are the same as in example 3.
Example 5
The difference from example 3 is that the power of the ultrasonic wave in step (2) was 100W, the frequency was 80kHz, and the other steps were the same as in example 3.
Example 6
The difference from example 3 is that the power of the ultrasonic wave in step (2) was 120W, the frequency was 40kHz, and the other steps were the same as in example 3.
Comparative example 1
The difference from example 3 is that the concentration of hydrofluoric acid in step (1) is 50%, the concentration of nitric acid is 68%, and the other steps are the same as in example 3.
Comparative example 2
The difference from example 3 is that the volume ratio of hydrofluoric acid and nitric acid in step (1) is 1:15, the other steps are the same as in example 3.
Comparative example 3
The difference from example 3 is that the etching time in step (1) was 10min, the total etching time in step (3) was 30min, and the other steps were the same as in example 3.
Comparative example 4
The difference from example 3 is that the etching time in step (1) was 0.5min, the total etching time in step (3) was 1min, and the other steps were the same as in example 3.
Comparative example 5
The difference from example 3 is that the acidic etching solution in step (1) is a mixed solution of hydrofluoric acid and hydrochloric acid, the concentration of hydrofluoric acid is 45%, the concentration of hydrochloric acid is 55%, and the volume ratio of hydrofluoric acid to hydrochloric acid to water is 2:13:50, the other steps are the same as in example 3.
Comparative example 6
The difference from example 3 is that the medical porous titanium alloy is directly immersed in a mixed solution of hydrofluoric acid, nitric acid and water for 16min, the concentration of hydrofluoric acid is 45%, the concentration of nitric acid is 55%, and the volume ratio of hydrofluoric acid, nitric acid and water is 2:5:50; taking out after 16min, cleaning for 3min by using an ultrasonic cleaner, and drying for later use.
Comparative example 7
The difference from comparative example 6 is that the volume ratio of hydrofluoric acid and nitric acid is 2:9, the other steps are the same as in comparative example 6.
Comparative example 8
The difference from comparative example 6 is that the volume ratio of hydrofluoric acid and nitric acid is 2:13, the other steps are the same as in comparative example 6.
Comparative example 9
The difference from comparative example 6 is that the volume ratio of hydrofluoric acid and nitric acid is 2:17, the other steps are the same as in comparative example 6.
Blank control group
The medical porous titanium alloy is not treated by any method.
Experiment
The samples of the medical porous titanium alloy treated by the above examples and comparative examples are subjected to uniaxial compression experiments respectively, and the experimental methods are as follows: the uniaxial compression test was performed using an electronic universal test instrument (UTM 5305; shenzhen, china) equipped with a load capacity of 100 KN. According to ISO13314:2011, the loading rate of the crosshead is set to 0.001/s-1. The compression experiment is carried out at room temperature (25 ℃), the test piece is compressed until fracture, a stress-strain average value curve is drawn, and mechanical parameters such as elastic modulus, compressive strength and the like are calculated according to the stress-strain curve. For each experimental group, three samples were tested and the average was calculated. The stress-strain average curves are shown in fig. 5, and the test results are shown in table 1.
TABLE 1
As can be seen from the analysis of the experimental data in table 1, the concentrations of hydrofluoric acid and nitric acid in comparative example 1 are too high, and excessive etching is liable to occur, so that the elastic modulus and compressive strength of the medical porous titanium alloy are greatly affected. The volume ratio of hydrofluoric acid to nitric acid in comparative example 2 is not within the scope of the application, and the elastic modulus and compressive strength of the medical porous titanium alloy are not as good as those of example 3, which indicates that the volume ratio of hydrofluoric acid to nitric acid does not adopt any proportion to achieve the effect of the application. The fractional etching time and total etching time in comparative examples 3 to 4 were not within the scope of the present application, and overetching was liable to occur, and the structure of the molded article was destroyed. Therefore, only by controlling the concentration, the volume ratio and the etching time of hydrofluoric acid and nitric acid within the range defined by the application, the adhering powder in the medical porous titanium alloy can be removed cleanly, and the mechanical property of the medical porous titanium alloy is ensured not to be reduced.
Comparative example 5 the medical porous titanium alloy was etched with other acidic etching solutions, the adhesion powder in the medical porous titanium alloy was not removed well, and the mechanical properties of the medical porous titanium alloy were also easily affected. Comparative example 6 the medical porous titanium alloy was treated by the direct immersion method, but the mechanical properties of the medical porous titanium alloy were lowered due to the long-term immersion in the acidic etching solution. Therefore, the medical porous titanium alloy is etched by adopting hydrofluoric acid and nitric acid, and the influence of the adhesive powder removal effect and the mechanical property in the medical porous titanium alloy can be balanced by adopting a method of combining graded chemical etching with ultrasonic cleaning.
As shown in fig. 3, in comparative examples 7 to 9, different volume ratios of hydrofluoric acid and nitric acid are respectively adopted, while the volume ratios of hydrofluoric acid and nitric acid in comparative examples 7 to 9 are all within the scope of the invention, in comparative examples 7 to 9, a direct soaking method is adopted to treat medical porous titanium alloy, the surface roughness of the medical porous titanium alloy is higher, more powder still adheres, the corrosion degree is insufficient, the sticky powder removing effect is not ideal, and meanwhile, as observed by an optical microscope, when the volume ratio of hydrofluoric acid to nitric acid is 2:17, the rod diameter of the medical porous titanium alloy after direct soaking is smaller than the original designed rod diameter, the porous structure is damaged, and the excessive corrosion phenomenon is found.
As shown in fig. 4, the diameter of the porous structure after LPBF forming is larger than the designed diameter, which indicates the existence of forming errors, and meanwhile, the surface and the side surface of the rod are covered with adhesive powder, which is the most main cause of the forming errors of the diameter of the rod, through observation of a scanning electron microscope.
From the experimental data of examples 1-6 and fig. 5, it can be seen that the post-graded etch beam diameter approaches the designed beam diameter size without excessive erosion, indicating no damage to the structure. The surface of the connecting rod after the graded etching is very smooth, has excellent forming quality, does not find defects such as pits, and the like, and the most of sticky powder on the surface and the side surface of the rod is corroded to a deeper degree and is uniformly corroded; the medical porous titanium alloy test piece after the combination of graded chemical etching and ultrasonic cleaning shows excellent mechanical properties, and the compressive strength and the elastic modulus are greatly improved. Meanwhile, the compressive strength and the elastic modulus are in the mechanical property range of human bone, and meet the requirements of bone implants.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The powder removing method for the medical porous titanium alloy manufactured by additive manufacturing is characterized by comprising the following steps of:
(1) Soaking medical porous titanium alloy in an acidic etching solution for 1-8min, and then taking out, wherein the acidic etching solution is a mixed solution of hydrofluoric acid, nitric acid and water, the concentration of the hydrofluoric acid is 35-45%, the concentration of the nitric acid is 55-65%, and the volume ratio of the hydrofluoric acid to the nitric acid to the water is (2-13): (2-13): 50;
(2) Cleaning the medical porous titanium alloy treated in the step (1) by adopting ultrasonic waves;
(3) Soaking the medical porous titanium alloy subjected to ultrasonic cleaning in the step (2) in the acid etching solution in the step (1) again for 1-8min, taking out, and cleaning again by adopting ultrasonic waves; repeating the step (1) and the step (2) until the total etching time is 2-16min;
(4) Drying the medical porous titanium alloy treated in the step (3), and taking out for later use;
The power of the ultrasonic wave in the step (2) is 100-2000W, and the frequency of the ultrasonic wave is 20-130kHz.
2. The method for removing powder from an additive manufactured medical porous titanium alloy according to claim 1, wherein in the step (1), the concentration of hydrofluoric acid is 45%, the concentration of nitric acid is 55%, and the volume ratio of hydrofluoric acid to nitric acid is 2: (5-13).
3. The method for removing powder from an additively manufactured medical porous titanium alloy according to claim 2, wherein the volume ratio of hydrofluoric acid to nitric acid in the step (1) is 2:12.
4. The method for removing powder from an additive manufactured medical porous titanium alloy according to claim 1, wherein the etching time in each of the step (1) and the step (3) is 1min.
5. The method for removing powder from an additive manufactured medical porous titanium alloy according to claim 1, wherein the total etching time in the step (3) is 16min.
6. The method for removing powder from an additive manufactured medical porous titanium alloy according to claim 1, wherein the power of the ultrasonic wave in the step (2) is 100 to 120W, and the frequency of the ultrasonic wave is 40 to 80kHz.
7. The method for removing powder from an additively manufactured medical porous titanium alloy according to claim 1, wherein the method for preparing the medical porous titanium alloy comprises the steps of:
(1) Adding titanium alloy powder into laser powder bed melting equipment, and opening an argon valve to ensure that the oxygen concentration in a working chamber is lower than 200ppm;
(2) After a model drawn by the three-dimensional modeling software is imported into an equipment computer, the process parameters of the laser melting technology are set as follows: the laser power is 30-400W, the exposure time is 5-300 mu s, the dot spacing is 5-400 mu m, the layer thickness is 20-100 mu m, and the laser beam is utilized to scan the melted powder layer by layer, so as to prepare the medical porous titanium alloy molding.
8. The method for removing powder from an additive manufactured porous titanium alloy for medical use according to claim 7, wherein the laser power in the step (2) is 250W, the exposure time is 50 μs, the dot pitch is 50 μm, the line pitch is 0.07mm, and the layer thickness is 50 μm.
9. Use of a medical porous titanium alloy in an orthopedic implant in the medical field, characterized in that the medical porous titanium alloy is obtained after the medical porous titanium alloy is treated by the powder removal method for manufacturing the medical porous titanium alloy by the additive according to any one of claims 1-8.
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| CN104027176A (en) * | 2013-03-07 | 2014-09-10 | 长庚医疗科技(厦门)有限公司 | Surface treated artificial bone material and its surface treatment method |
| CN109261958A (en) * | 2018-11-15 | 2019-01-25 | 西北有色金属研究院 | Surface coats the medical porous titanium of tantalum coating or the preparation method of titanium alloy material |
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| CN104027176A (en) * | 2013-03-07 | 2014-09-10 | 长庚医疗科技(厦门)有限公司 | Surface treated artificial bone material and its surface treatment method |
| CN109261958A (en) * | 2018-11-15 | 2019-01-25 | 西北有色金属研究院 | Surface coats the medical porous titanium of tantalum coating or the preparation method of titanium alloy material |
| CN110000382A (en) * | 2019-04-25 | 2019-07-12 | 中国科学院金属研究所 | The minimizing technology of support construction in a kind of increasing material manufacturing titanium alloy |
| CN112999414A (en) * | 2021-02-07 | 2021-06-22 | 大博医疗科技股份有限公司 | 3D printing titanium alloy and preparation method thereof |
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