CN111926340B - Cleaning method for 3D printing titanium and titanium alloy - Google Patents
Cleaning method for 3D printing titanium and titanium alloy Download PDFInfo
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- CN111926340B CN111926340B CN202010809626.2A CN202010809626A CN111926340B CN 111926340 B CN111926340 B CN 111926340B CN 202010809626 A CN202010809626 A CN 202010809626A CN 111926340 B CN111926340 B CN 111926340B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/08—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for polishing surfaces, e.g. smoothing a surface by making use of liquid-borne abrasives
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
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- 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
- B08B3/02—Cleaning by the force of jets or sprays
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- 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
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0035—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like
- B08B7/0057—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like by ultraviolet radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/04—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by a combination of operations
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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
- B22F10/68—Cleaning or washing
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- 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
- B33Y40/10—Pre-treatment
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/28—Bones
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2002/3092—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth having an open-celled or open-pored structure
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- 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
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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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
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- 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
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- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- ing And Chemical Polishing (AREA)
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- Prostheses (AREA)
Abstract
The invention belongs to the field of surface treatment of 3D printing titanium and titanium alloy, and relates to a cleaning method of the 3D printing titanium and the 3D printing titanium alloy, which comprises the steps of sequentially carrying out cleaning and oil removal, sand blasting, high-pressure washing, plasma cleaning and/or ultraviolet light cleaning and corrosion cleaning on the 3D printing titanium and the 3D printing titanium alloy, wherein a corrosion solution adopted by the corrosion cleaning contains a corrosive agent and an additive, the balance is water, the corrosive agent is selected from at least one of sulfuric acid, hydrochloric acid, oxalic acid, nitric acid and hydrofluoric acid, the additive is selected from at least one of methanol, ethanol and a surfactant, and the additive is rinsed and dried by pure water. By adopting the method provided by the invention, the powder particles and the cutting media remained in the porous layer and the grid structure of the 3D printing product can be completely removed.
Description
Technical Field
The invention belongs to the field of surface treatment of 3D printing titanium and titanium alloy, and particularly relates to a cleaning method of 3D printing titanium and titanium alloy.
Background
The titanium and titanium alloy 3D printed product is formed by melting and cooling titanium and titanium alloy powder through electron beams or laser to form metal bonds, generating a stable semi-finished product with certain strength, structure and function, and then forming a final 3D printed product which meets the dimensional accuracy and expected functions through machining. The 3D printed implant provides a robust and effective mechanical and biological support for promoting bone tissue growth and for creating effective bone ingrowth and bone ingrowth effects between the implant and the bone tissue of the human body. Compared with the traditional machining mode, the 3D printing implant can construct a shape which is more complex and more suitable for various bones in a human body, and can directly construct a porous layer or a mesh structure with a special porous structure so as to be beneficial to bone ingrowth and bone growth.
According to the process characteristics of 3D printing and post-processing, in the process of melting titanium and titanium alloy powder by energy such as electron beams or laser, the powder in the porous layer and the mesh structure can be divided into two types according to the combination state, wherein one type is unfused free particles which are mixed in the porous structure, and the other type is partially melted and is in metal bonding adhesion with the surrounding porous surface, and the two types of combination state enable titanium and titanium alloy powder particles to be greatly mixed in the porous layer and the mesh structure. If these powder particles are not completely removed from the titanium and titanium alloy implants, they may be scattered around the implants after long-term storage in the human environment, causing a corresponding inflammatory reaction and even being life-threatening, with a high risk. In addition, in the post-3D printing process, a large amount of cooling medium containing oil-based cutting fluid or water-based cutting fluid is used for machining auxiliary cooling and cutting treatment, and at this time, the cooling medium is attached to the surface of the porous layer or the mesh structure in a large amount, and if the cleaning is not thorough, there is a great risk, and the implantation effect is finally affected, or even the life safety is affected.
The conventional cleaning method for titanium and titanium alloy powder in a 3D printing product is mainly sand blasting cleaning or high-pressure washing, and residual 3D printing powder particles attached to the surface are removed through the impact effect of sand grains or high-speed water. However, the two modes have certain defects, on one hand, the two action modes have directionality, the cleaning and removing effects on the opposite vertical surfaces of sand grains and high-speed water are good, but the impact action on the adjacent inclined surfaces or the back surfaces is limited, and particularly, more products are processed by using a 3D printing technology to obtain complex shapes or porous structures instead of planes, so that the defects of the two cleaning modes become more prominent; on the other hand, the porous layer or the mesh with the porous structure formed by 3D printing is generally a non-thin layer but has a certain thickness, so that sand grains and high-speed water are difficult to enter the internal structure, or the impact cleaning effect is achieved only a few millimeters away from the surface layer, which is more expressed in that a large amount of impact energy is consumed in the process of entering the internal structure, the impact effect is greatly reduced, and residual powder particles in the internal structure cannot be completely removed. Similarly, the cleaning mode for the machining cutting medium remaining in the 3D printed product is mainly ultrasonic cleaning, but in actual production, it is found that, because the 3D printed porous structure is different from a conventional processing structure, the 3D printed porous structure has more microstructures and micropores, so that even under the action of ultrasonic waves, bubbles existing in the microstructures and the micropores cannot be expelled in time and thoroughly, and the cleaning agent cannot thoroughly infiltrate all surfaces, especially surfaces of complex micropores, resulting in the residue of the cutting medium in the internal structure.
Disclosure of Invention
The invention aims to overcome the defect that the powder particles and cutting media remained in the porous layer and the mesh structure of the 3D printing titanium and titanium alloy cannot be completely removed by adopting the conventional cleaning mode, and provides a cleaning method capable of completely removing the powder particles and cutting media remained in the porous layer and the mesh structure of the 3D printing titanium and titanium alloy.
In order to achieve the above object, the present invention provides a cleaning method for 3D printing titanium and titanium alloy, comprising:
s1, cleaning and deoiling the 3D printing titanium and the titanium alloy to obtain deoiled 3D printing titanium and the deoiled titanium alloy;
s2, carrying out sand blasting treatment and high-pressure washing on the deoiled 3D printed titanium and titanium alloy in sequence to obtain primary cleaned 3D printed titanium and titanium alloy;
s3, carrying out plasma cleaning and/or ultraviolet cleaning on the primary cleaning 3D printing titanium and titanium alloy to obtain secondary cleaning 3D printing titanium and titanium alloy;
s4, performing corrosion cleaning on the secondary cleaning 3D printing titanium and the titanium alloy by using a corrosion solution, wherein the corrosion solution contains a corrosive agent and an additive, the balance is water, the corrosive agent is selected from at least one of sulfuric acid, hydrochloric acid, oxalic acid, nitric acid and hydrofluoric acid, the additive is selected from at least one of methanol, ethanol and a surfactant, and then rinsing by using pure water and drying.
In the invention, the 3D printing titanium and titanium alloy is a titanium and titanium alloy semi-finished product obtained by performing heat treatment and machining on titanium and titanium alloy powder after 3D printing and forming.
In the invention, a large amount of titanium and titanium alloy powder particles and cooling media are remained in the porous layer and the mesh structure on the surface of the 3D printing titanium and titanium alloy.
In the present invention, in step S1, the purpose of the cleaning and degreasing is to remove residual grease on the surface of the 3D printing titanium and titanium alloy. The cleaning and degreasing method can be, for example, placing 3D printed titanium and titanium alloy in a cleaning solution containing a surfactant, and performing ultrasonic treatment at 60-70 ℃ for 5-20 min.
In the present invention, in step S2, the purpose of the sand blasting and the high pressure washing is to remove the impurities of the free powder particles and the partially fused particles in the porous structure of the surface of the 3D printed titanium and titanium alloy. The grain size of the sand adopted by the sand blasting treatment is preferably 80-1000 meshes, and the grain size is just matched with the porous structure on the surface of the 3D printing titanium and titanium alloy product, so that powder particles mixed in the porous structure can be effectively removed by spraying. In addition, the sand may be ceramic sand, titanium sand, or a mixture of the two. In a preferred embodiment, the conditions of the sand blasting treatment include a sand blasting pressure of 3 to 6bar and a sand blasting distance of 10 to 20 cm. In another preferred embodiment, the high-pressure washing conditions include a high-speed water injection pressure of 100 to 500bar and a washing time of 60 to 1200 s. Furthermore, the high-pressure flushing is preferably rotary high-pressure flushing, i.e. the high-speed water flow rotates clockwise or counterclockwise during the flushing process.
In the present invention, in step S3, the purpose of the plasma cleaning and/or the ultraviolet light cleaning is mainly to remove carbon-containing organic matters on the surface and obtain a clean super-hydrophilic surface. In a preferred embodiment, the plasma cleaning method is vacuum plasma cleaning, and the specific conditions include using a mixed gas of argon and oxygen, the flow rate of argon is 0 to 450sccm, the flow rate of oxygen is 0 to 200sccm, the vacuum degree is-99.5 KPa, the processing time is 60 to 600s, and the cleaning power is 0 to 700W. In another preferred embodiment, the ultraviolet light cleaning conditions include an ultraviolet light wavelength of 180 to 260nm, an irradiation distance of 0.5 to 5cm, and an irradiation time of 5 to 30 min.
In the present invention, in step S4, the purpose of the etching cleaning process is mainly to remove partially melted particles that are partially melted in the porous structure on the surface of the 3D printed titanium or titanium alloy and are bonded to the surrounding porous surface by metal bonding, and oil-soluble and water-soluble residual substances that are stripped off during the etching gas generation process. The corrosive liquid contains a corrosive agent and an additive, and the balance is water. Wherein the etchant is selected from at least one of sulfuric acid, hydrochloric acid, oxalic acid, nitric acid and hydrofluoric acid. The additive is selected from at least one of ethanol, methanol and a surfactant. The surfactant is at least one selected from the group consisting of a sulfate type surfactant, a sulfonate type surfactant, a carboxylate type surfactant and a quaternary ammonium salt type surfactant. In a preferred embodiment, the content of the single component of the corrosive agent in the corrosive liquid is 1-70 wt%, and the content of the single component of the additive is 0.1-5 wt%. In another preferred embodiment, the etching cleaning conditions include a temperature of 60 to 90 ℃ and a time of 20 to 60 min. In addition, the etching cleaning process is preferably performed under ultrasonic oscillation or bubbling conditions.
According to the invention, through a specific combined cleaning mode, the surface porous layer formed by 3D printing of titanium and titanium alloy, the powder particles in the grid structure and the cutting medium can be effectively removed, bubbles existing in a specific microstructure and micropores are timely and thoroughly expelled, and the infiltration corrosion effect is more thorough.
Furthermore, after cleaning and oil removal, sand blasting, high-pressure flushing, plasma cleaning and/or ultraviolet light cleaning, the invention adopts a special corrosion mode to remove the residual powder particles in the printing process and the residual oil-soluble and water-soluble residual substances on the stripping surface in the gas generating corrosion process, thereby solving the problems that the internal treatment difficulty of the porous layer or the mesh structure is high, and the bubbles in the microstructure and the micropores can not be completely removed, so that the cleaning agent can not completely infiltrate all surfaces, especially the surfaces of the complicated micropores, and the cutting medium in the internal structure is remained. In addition, in the corrosion cleaning process, a specific corrosion system is adopted, so that the corrosion speed is stable and controllable, the defects of excessive corrosion and poor corrosion removal effect can be effectively prevented, the integral and microscopic sizes after cleaning are ensured to be within a preset range, and the integral and microscopic mechanical strength and biological osteogenesis effect are ensured.
Drawings
FIG. 1 is a SEM image of the surface of a 3D printed Ti or Ti alloy after heat treatment (high temperature annealing) in example 1;
FIG. 2 is an SEM image of the surface of 3D-printed titanium and titanium alloy of example 1 after sand blasting and high-pressure washing, wherein A is an overall appearance image magnified 65 times and B is a partial appearance image magnified 500 times;
FIG. 3 is a surface water contact angle chart of the titanium and titanium alloy after UV irradiation in 3D printing in example 1;
fig. 4 is an SEM image of the surface of the 3D-printed titanium and titanium alloy after corrosion drying treatment in example 1, where a is an overall appearance image enlarged by 50 times, and B is a partial appearance image enlarged by 500 times;
FIG. 5 is a graph showing the mass change of 3D-printed titanium and titanium alloy of example 1 before and after etching at different times;
FIG. 6 is a SEM image of a surface of 3D printed titanium and titanium alloys that has been conventionally treated (sand blasted only);
fig. 7 is a surface SEM image of 3D printed titanium and titanium alloys that were conventionally treated (high pressure rinse only).
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
According to expected requirements, carrying out 3D printing forming on titanium alloy powder to obtain a semi-finished product of the acetabular cup with a corresponding structure and shape, then carrying out high-temperature annealing treatment, carrying out wire cutting separation on a connecting area and carrying out hole machining treatment on a printed sample to obtain the 3D printed titanium and titanium alloy acetabular cup. The surface SEM image of the acetabulum cup of the 3D printed titanium and titanium alloy after the high-temperature annealing treatment is shown in FIG. 1. As can be seen from fig. 1, there are a number of free and semi-molten microspheroidal particles and cooling media present in the porous layer of the 3D printed titanium and titanium alloy acetabular cup surfaces as well as in the mesh structure.
Cleaning the 3D printed titanium and titanium alloy acetabular cup in the following way:
s1, placing the 3D printed titanium and titanium alloy acetabular cup in a detergent water solution containing 5% of a surfactant (specifically PWC-401 detergent, the same below), and ultrasonically removing oil and cleaning for 10min in an ultrasonic groove at 65 ℃ to remove residual oil on the surface to obtain the oil-removed 3D printed titanium and titanium alloy acetabular cup.
S2, performing sand blasting treatment on the surface of the oil-removing 3D printing titanium and titanium alloy acetabular cup by using 608-mesh ceramic sand to remove free powder particle impurities and partial fused particles in the porous structure, wherein the sand blasting pressure is 6bar, and the sand blasting distance is 20 cm; and then, carrying out rotary high-pressure washing treatment on the surface of the acetabulum cup by adopting 300kg of filtered high-speed water, wherein the injection pressure of the high-speed water is 300bar, and the washing time is 1200s, so as to obtain a first-stage washing 3D printing titanium and titanium alloy acetabulum cup. An SEM image of the surface of the primary cleaning 3D printed titanium and titanium alloy acetabular cup is shown in FIG. 2, wherein A is an overall appearance image magnified by 65 times, and B is a partial appearance image magnified by 500 times. As can be seen from FIG. 2, semi-molten microspheres in the internal structure of the primary cleaning 3D printing titanium and titanium alloy acetabular cup are not completely removed.
S3, the primary-cleaning 3D printing titanium and titanium alloy acetabular cup is cleaned through ultraviolet irradiation, the wavelength of ultraviolet light irradiated by the ultraviolet light is 180-260 nm, the irradiation near-end distance is 0.5cm, and the irradiation time is 30min, so that the secondary-cleaning 3D printing titanium and titanium alloy acetabular cup is obtained. The surface water contact angle diagram of the two-stage cleaning 3D printed titanium and titanium alloy acetabular cup is shown in FIG. 3. As can be seen from fig. 3, the water drop was completely spread out in contact with the surface at an instant, and the contact angle was not measured, which was almost 0 °.
S4, after irradiation is completed, rapidly immersing the processed two-stage cleaning 3D printing titanium and titanium alloy acetabulum cup into corrosive liquid for corrosion cleaning, wherein the corrosive liquid contains corrosive agents and additives, and the balance is water; the corrosive agent is a mixed solution of sulfuric acid and hydrochloric acid, the mass fraction of the sulfuric acid is 30%, and the mass fraction of the hydrochloric acid is 1%; the additive is a mixed additive of ethanol and a surfactant, the mass fraction of the ethanol is 5%, the surfactant is sodium tetradecyl sulfate, and the mass fraction of the surfactant is 0.1%; the corrosion temperature is 80 ℃, the corrosion time is 30min, and the corrosion process is carried out under the bubbling condition. And (5) drying for later use after rinsing with purified water.
The surface SEM image of the etched and dried acetabular cup product is shown in fig. 4, where a is the overall appearance image at 50 times magnification and B is the partial appearance image at 500 times magnification. As can be seen from fig. 4, there are no residual free particles and semi-molten particles printed by 3D printing on the surface and the inner hole after the treatment, and the surface and the inner hole have uniform appearance. The mass change curve of the acetabular cup product before and after the erosion treatment is shown in fig. 5. As can be seen from FIG. 5, the corrosion rate of the present invention is stable and controllable.
Example 2
According to expected requirements, carrying out 3D printing forming on titanium alloy powder to obtain a semi-finished product of the acetabular cup with a corresponding structure and shape, then carrying out high-temperature annealing treatment, carrying out wire cutting separation on a connecting area and carrying out hole machining treatment on a printed sample to obtain the 3D printed titanium and titanium alloy acetabular cup. As can be seen by SEM, there are a large number of free and semi-molten microspheroidal particles and cooling medium in the porous layer and the mesh structure on the surface of the 3D printed titanium and titanium alloy acetabular cup.
Cleaning the 3D printed titanium and titanium alloy acetabular cup in the following way:
s1, placing the 3D printing titanium and titanium alloy acetabular cup into a detergent water solution containing 5% of surfactant, and ultrasonically degreasing and cleaning for 10min in an ultrasonic groove at 65 ℃ to remove residual grease on the surface, so as to obtain the degreased 3D printing titanium and titanium alloy acetabular cup.
S2, performing sand blasting treatment on the surface of the oil-removing 3D printing titanium and titanium alloy acetabular cup by using 80-mesh titanium sand to remove free powder particle impurities and partial molten particles in a porous structure, wherein the sand blasting pressure is 3bar, and the sand blasting distance is 10 cm; and then, carrying out rotary high-pressure washing treatment on the surface of the acetabulum cup by adopting 300kg of filtered high-speed water, wherein the spraying pressure of the high-speed water is 500bar, and the washing time is 60s, thus obtaining the primary washing 3D printing titanium and titanium alloy acetabulum cup. As can be seen from SEM, semi-molten microspheres in the inner structure of the primary cleaning 3D printing titanium and titanium alloy acetabular cup are not completely removed.
S3, cleaning the primary-cleaning 3D-printed titanium and titanium alloy acetabular cup by vacuum plasma, wherein the specific conditions include that a mixed gas of argon and oxygen is adopted, the flow of argon is 200sccm, the flow of oxygen is 100sccm, the vacuum degree is-99.5 KPa, the processing time is 200S, and the cleaning power is 300W, so that the secondary-cleaning 3D-printed titanium and titanium alloy acetabular cup is obtained. The surface water contact angle of the two-stage cleaning 3D printing titanium and titanium alloy acetabular cup is almost 0 degrees.
S4, after irradiation is completed, rapidly immersing the processed two-stage cleaning 3D printing titanium and titanium alloy acetabulum cup into corrosive liquid for corrosion cleaning, wherein the corrosive liquid contains corrosive agents and additives, and the balance is water; the corrosive agent is a mixed solution of oxalic acid, nitric acid and hydrofluoric acid, wherein the mass fraction of the oxalic acid is 70%, the mass fraction of the nitric acid is 1%, and the mass fraction of the hydrofluoric acid is 10%; the additive is a mixed additive of methanol and ethanol, wherein the mass fraction of the methanol is 1%, and the mass fraction of the ethanol is 5%; the corrosion temperature is 80 ℃, the corrosion time is 20min, and the corrosion process is carried out under the bubbling condition. And (5) drying for later use after rinsing with purified water. According to SEM, the surface and the inner hole of the acetabulum cup product subjected to corrosion drying treatment are smooth and uniform, and free particles and semi-molten particles which are printed in a 3D mode are not left.
Example 3
According to expected requirements, carrying out 3D printing forming on titanium alloy powder to obtain a semi-finished product of the acetabular cup with a corresponding structure and shape, then carrying out high-temperature annealing treatment, carrying out wire cutting separation on a connecting area and carrying out hole machining treatment on a printed sample to obtain the 3D printed titanium and titanium alloy acetabular cup. As can be seen from SEM, a large amount of free and semi-molten microsphere particles and cooling media exist in the porous layer on the surface of the 3D printing titanium and titanium alloy acetabular cup and the mesh structure.
Cleaning the 3D printed titanium and titanium alloy acetabular cup in the following way:
s1, placing the 3D printing titanium and titanium alloy acetabular cup into a detergent water solution containing 5% of surfactant, and ultrasonically degreasing and cleaning for 10min in an ultrasonic groove at 65 ℃ to remove residual grease on the surface, so as to obtain the degreased 3D printing titanium and titanium alloy acetabular cup.
S2, performing sand blasting treatment on the surface of the oil-removing 3D printing titanium and titanium alloy acetabular cup by using 80-mesh titanium sand to remove free powder particle impurities and partial molten particles in a porous structure, wherein the sand blasting pressure is 3bar, and the sand blasting distance is 10 cm; and then, carrying out rotary high-pressure washing treatment on the surface of the acetabulum cup by adopting 300kg of filtered high-speed water, wherein the spraying pressure of the high-speed water is 100bar, and the washing time is 800s, thus obtaining the primary washing 3D printing titanium and titanium alloy acetabulum cup. As can be seen from SEM, semi-molten microspheres in the inner structure of the primary cleaning 3D printing titanium and titanium alloy acetabular cup are not completely removed.
S3, the primary cleaning 3D printing titanium and titanium alloy acetabular cup is cleaned through ultraviolet irradiation, the wavelength of ultraviolet light irradiated is 180-260 nm, the irradiation near-end distance is 5cm, and the irradiation time is 30min, so that the secondary cleaning 3D printing titanium and titanium alloy acetabular cup is obtained, and the secondary cleaning 3D printing titanium and titanium alloy acetabular cup is obtained. The surface water contact angle of the two-stage cleaning 3D printing titanium and titanium alloy acetabular cup is almost 0 degrees.
S4, after irradiation is completed, rapidly immersing the processed two-stage cleaning 3D printing titanium and titanium alloy acetabulum cup into corrosive liquid for corrosion cleaning, wherein the corrosive liquid contains corrosive agents and additives, and the balance is water; the corrosive agent is sulfuric acid, the additive is ethanol, the mass fraction of the sulfuric acid is 50%, and the mass fraction of the ethanol is 2%; the corrosion temperature is 90 ℃, the corrosion time is 30min, and the corrosion process is carried out under the bubbling condition. And (5) drying for later use after rinsing with purified water. According to SEM, the surface and inner holes of the acetabulum cup product subjected to corrosion drying treatment are smooth and uniform, and free particles and semi-molten particles printed in a 3D mode are not left.
Comparative example 1
Cleaning the 3D printed titanium and titanium alloy according to the method of example 1, except that in step S2, only the surface of the acetabulum cup of degreased titanium and titanium alloy is subjected to sand blasting, and steps S3 and S4 are not included, and the surface SEM image of the obtained 3D printed titanium and titanium alloy is shown in FIG. 6. As can be seen from the results of fig. 6, the internal structure of the product obtained with the conventional treatment (sand blasting only) had semi-molten microspheres that were not completely removed.
Comparative example 2
Cleaning the 3D printed titanium and titanium alloy according to the method of example 1, except that in step S2, only the surface of the acetabulum cup of degreased titanium and titanium alloy is washed under high pressure, and steps S3 and S4 are not included, and the surface SEM image of the obtained 3D printed titanium and titanium alloy is shown in FIG. 7. As can be seen from the results of fig. 7, the internal structure of the product obtained with the conventional treatment (high pressure washing only) had semi-molten microspheres that were not completely removed.
Comparative example 3
Cleaning 3D printed titanium and titanium alloy according to the method of the embodiment 1, except that the steps S2 and S3 are exchanged, namely, ultraviolet irradiation cleaning is firstly carried out, then sand blasting treatment and rotary high-pressure washing treatment are carried out, and the other conditions are the same as the embodiment 1, so that the acetabular cup product is obtained. As can be seen from SEM, although the outermost surface of the acetabular cup product is clean and uniform and has no particle residues, part of fused particles remain in the deep hole structure inside, particularly in the recessed area of the inner hole, and cannot be completely removed.
Comparative example 4
Cleaning the 3D printed titanium and titanium alloy according to the method of the embodiment 1, except that oxalic acid with the same mass fraction is used for replacing the adopted corrosive liquid in the step S4, and the other conditions are the same as the embodiment 1, so as to obtain the acetabular cup product. As can be seen from SEM, both the surface and the inner deep hole structure of the acetabular cup product have unmelted and partially melted particle residues, which cannot be completely removed.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that those skilled in the art may make variations, modifications, substitutions and alterations within the scope of the present invention without departing from the spirit and scope of the present invention.
Claims (9)
1. A cleaning method for 3D printing titanium and titanium alloy is characterized by comprising the following steps:
s1, cleaning and deoiling the 3D printing titanium and the titanium alloy to obtain deoiled 3D printing titanium and the deoiled titanium alloy;
s2, carrying out sand blasting treatment and high-pressure washing on the oil-removing 3D printing titanium and titanium alloy in sequence to obtain primary cleaning 3D printing titanium and titanium alloy;
s3, carrying out plasma cleaning and/or ultraviolet cleaning on the primary cleaned 3D printed titanium and titanium alloy to obtain secondary cleaned 3D printed titanium and titanium alloy;
s4, performing corrosion cleaning on the secondary-cleaning 3D printed titanium and titanium alloy by using a corrosion solution, wherein the corrosion solution contains a corrosive agent and an additive, the balance is water, the corrosive agent is selected from at least one of sulfuric acid, hydrochloric acid, oxalic acid, nitric acid and hydrofluoric acid, the additive is selected from at least one of methanol, ethanol and a surfactant, rinsing by using pure water and then drying, and the corrosion cleaning process is performed under the condition of ultrasonic oscillation or bubbling;
the 3D printing titanium and titanium alloy is a titanium and titanium alloy semi-finished product obtained by performing heat treatment and machining on titanium and titanium alloy powder after 3D printing and forming; titanium and titanium alloy powder particles and cooling media are left in the porous layer on the surface of the 3D printing titanium and titanium alloy and the mesh grid structure.
2. The cleaning method for 3D printed titanium and titanium alloys according to claim 1, wherein in step S1, the cleaning and degreasing method comprises the steps of placing the 3D printed titanium and titanium alloys in a cleaning solution containing a surfactant, and performing ultrasonic treatment at 60-70 ℃ for 5-20 min.
3. The cleaning method for 3D printing titanium and titanium alloy according to claim 1, wherein in step S2, the sand used in the sand blasting is ceramic sand and/or titanium sand of 80-1000 meshes; the conditions of the sand blasting treatment comprise that the sand blasting pressure is 3-6 bar and the sand blasting distance is 10-20 cm.
4. The cleaning method for 3D printing titanium and titanium alloy according to claim 1, wherein in step S2, the high pressure washing conditions include a high speed water jet pressure of 100-500 bar and a washing time of 60-1200S.
5. The cleaning method for 3D printing titanium and titanium alloy according to claim 1, wherein in step S3, the plasma cleaning method is vacuum plasma cleaning, and the specific conditions include using a mixed gas of argon and oxygen, the flow rate of argon is 0-450 sccm, the flow rate of oxygen is 0-200 sccm, the vacuum degree is-99.5 KPa, the processing time is 60-600S, and the cleaning power is 0-700W.
6. The cleaning method for 3D printing titanium and titanium alloy according to claim 1, wherein in step S3, the conditions of the ultraviolet light cleaning include that the wavelength of the ultraviolet light is 180-260 nm, the irradiation distance is 0.5-5 cm, and the irradiation time is 5-30 min.
7. The cleaning method for 3D printed titanium and titanium alloys according to claim 1, wherein in step S4, the surfactant contained in the etching solution is at least one selected from the group consisting of a sulfate surfactant, a sulfonate surfactant, a carboxylate surfactant and a quaternary ammonium surfactant.
8. The method for cleaning 3D printed titanium and titanium alloy according to claim 1, wherein the content of the single component of the corrosive agent in the corrosive solution is 1-70 wt%, and the content of the single component of the additive is 0.1-5 wt%.
9. The cleaning method for 3D printed titanium and titanium alloys according to claim 1, wherein said etching cleaning conditions include temperature of 60-90 ℃ for 20-60 min.
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| CN114681672A (en) * | 2020-12-29 | 2022-07-01 | 中国科学院上海硅酸盐研究所 | Titanium alloy biological function stent and preparation method and application thereof |
| CN112877702A (en) * | 2021-01-13 | 2021-06-01 | 西安航天发动机有限公司 | Method for removing powder particles of titanium alloy interlayer narrow flow passage component |
| JP2022136707A (en) * | 2021-03-08 | 2022-09-21 | 新東工業株式会社 | Surface processing method |
| CN113210362B (en) * | 2021-03-25 | 2022-08-09 | 广东工业大学 | Cleaning method for antibacterial surface of alloy microstructure |
| CN113814418B (en) * | 2021-08-05 | 2022-10-28 | 珠海乔丹科技股份有限公司 | Surface treatment process of titanium or titanium alloy dental implant |
| CN114769577A (en) * | 2022-03-15 | 2022-07-22 | 温州伟达贵金属粉体材料有限公司 | Preparation method of high-dispersion micron-sized silver powder for electrical contact |
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