CN110037813A - A kind of titanium-based zirconium oxide composite material medical implant and its 3D printing preparation method - Google Patents
A kind of titanium-based zirconium oxide composite material medical implant and its 3D printing preparation method Download PDFInfo
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- CN110037813A CN110037813A CN201910332175.5A CN201910332175A CN110037813A CN 110037813 A CN110037813 A CN 110037813A CN 201910332175 A CN201910332175 A CN 201910332175A CN 110037813 A CN110037813 A CN 110037813A
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000007943 implant Substances 0.000 title claims abstract description 53
- 239000010936 titanium Substances 0.000 title claims abstract description 53
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 53
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 51
- 238000010146 3D printing Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 139
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000919 ceramic Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000010355 oscillation Effects 0.000 claims abstract description 11
- 238000005411 Van der Waals force Methods 0.000 claims abstract description 5
- 238000009825 accumulation Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000005253 cladding Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 239000006104 solid solution Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 20
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 5
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 229910001040 Beta-titanium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000004053 dental implant Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002682 general surgery Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 230000000771 oncological effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
-
- 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
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Cardiology (AREA)
- Epidemiology (AREA)
- Transplantation (AREA)
- Dentistry (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Vascular Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Prostheses (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of titanium-based zirconium oxide composite material medical implant and its 3D printing preparation methods, are related to metal laser selective melting (SLM) technical field.This method includes by nanometer ZrO2Ceramic powder is mixed with default powder, obtains a nanometer ZrO2Powder coats the uniform composite powder of default powder；Default powder and nanometer ZrO2Ceramic powder mixes under energy oscillation, for breaking a nanometer ZrO2Van der Waals force between ceramic powder；3D printing is carried out after uniform composite powder is mixed with titanium alloy powder.This method can have both excellent human compatibility and comprehensive mechanical property, and stock utilization is high, keep the part accuracy obtained by the Method of printing high, and consistency is high, and anti-corrosion abrasion resistance is good.Default powder can be the metal powder that nickel, cobalt etc. form solid solution with titanium alloy.Meanwhile by adjusting nanometer ZrO2The dosage of ceramic powder designs the microstructure of implant surfaces, the product of also customizable different mechanical properties.
Description
Technical field
The present invention relates to metal laser selective melting (SLM) technical fields, and in particular to a kind of titanium-based zirconium oxide is compound
Material medical implant and its 3D printing preparation method.
Background technique
3D printing technique is one kind of rapid shaping technique, is a kind of increases material manufacturing technology, combines computer science, essence
All various cutting edge technologies such as close manufacturing technology, material science, electronic laser beam.It is utilized using discrete-accumulation principle
CAD/CAM creates threedimensional model, then is sliced with Slice Software, successively printing superposition, final integrally formed.The technology part accuracy
High, product consistency height, stock utilization are high, are one of the developing direction of prospective material forming technique.
In recent years, 3D printing technique mainly includes general surgery, outside oral cavity in medical field using more and more extensive
Section, Oncological Surgery, prosthese, organ transplant and medical teaching etc..Manufacturing process mainly has: precinct laser fusion
(Selective Laser Melting, SLM), stereo lithography (Stereolithography), melt deposition molding
(Fused Deposition Modeling, FDM) etc..Wherein, the dentistry of selective laser fusing (SLM) preparation, bone material are comprehensive
Good mechanical properties are closed, being mutually matched property is excellent, just by the extensive concern of domestic and foreign scholars.
Studies have shown that titanium alloy has good mechanical property and biocompatibility, led in current Medical orthopaedic, dentistry
Domain is the most common bone implant and dental implant material using extremely wide.And ZrO2Ceramics have wearability good, biological
Compatibility is better than the advantages that various metal alloys, is a kind of ideal titanium-based zirconium oxide composite material medical implant material, choosing
Composite material 3D printing orthopaedics, the dental implant formed with two kinds of materials of titanium alloy and zirconia ceramics, can have both excellent
Mechanical property, biocompatibility.But titanium alloy and zirconium oxide interfacial reaction are difficult, and the characteristic of wetability difference limits its development.
Summary of the invention
The purpose of the present invention is to provide a kind of 3D printing preparation method of titanium-based zirconium oxide composite material medical implant,
This method prints titanium-based zirconium oxide composite material medical implant using titanium-based zirconium oxide composite material, can have both excellent people
Compatability and comprehensive mechanical property, stock utilization is high, so that, consistency high by the part accuracy that the Method of printing obtains
Height, anti-corrosion abrasion resistance are good.Meanwhile by changing implant microstructure and nanometer ZrO2The content of ceramic powder is also customizable
The product of different mechanical properties.
Another object of the present invention is to provide a kind of titanium-based zirconium oxide composite material medical implant, the titanium-based zirconium oxides
Composite material medical implant is prepared by the 3D printing preparation method of above-mentioned titanium-based zirconium oxide composite material medical implant
It obtains.Therefore, the precision, consistency of the titanium-based zirconium oxide composite material medical implant are high, and anti-corrosion wear resistence is good, has both human body
Compatibility and excellent comprehensive mechanical property.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of 3D printing preparation method of titanium-based zirconium oxide composite material medical implant comprising:
By nanometer ZrO2Ceramic powder is mixed with default powder, obtains a nanometer ZrO2Powder coats the uniform multiple of default powder
Close powder；Wherein, mixing is for breaking a nanometer ZrO under energy oscillation2Van der Waals force between ceramic powder；
3D printing is carried out after uniform composite powder is mixed with titanium alloy powder.
The present invention proposes a kind of titanium-based zirconium oxide composite material medical implant, compound by above-mentioned titanium-based zirconium oxide
The 3D printing preparation method of material medical implant is prepared.
The titanium-based zirconium oxide composite material medical implant of the embodiment of the present invention and its beneficial effect of 3D printing preparation method
Fruit is:
The 3D printing preparation method of titanium-based zirconium oxide composite material medical implant that the embodiment of the present invention provides includes
By nanometer ZrO2Ceramic powder is mixed with default powder, obtains a nanometer ZrO2Powder coats the uniform composite powder of default powder；Its
In, preset powder and nanometer ZrO2Ceramic powder mixes under energy oscillation, for breaking a nanometer ZrO2Model moral between ceramic powder
Hua Li；3D printing is carried out after uniform composite powder is mixed with titanium alloy powder.This method joined the default powder such as nickel or cobalt,
Make it that can form preferably infiltration with zirconia ceramics and connect, can be used as transition metal, reduces the two and combine difficulty, thus
Precision and the higher product of consistency is prepared in the consistency that material can be improved.Meanwhile this method is multiple using titanium-based zirconium oxide
Condensation material prints titanium-based zirconium oxide composite material medical implant, can have both excellent human compatibility and comprehensive mechanical property
Can, stock utilization is high.The part accuracy obtained by the Method of printing is high, and consistency is high, and anti-corrosion abrasion resistance is good.Also,
By changing implant microstructure and nanometer ZrO2The product of the also customizable different mechanical properties of the content of ceramic powder.
The embodiments of the present invention also provide a kind of titanium-based zirconium oxide composite material medical implant, the titanium-based zirconium oxide is multiple
Condensation material medical implant is prepared by the 3D printing preparation method of above-mentioned titanium-based zirconium oxide composite material medical implant
It arrives.Therefore, the precision and consistency of the titanium-based zirconium oxide composite material medical implant are high.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to the titanium-based zirconium oxide composite material medical implant of the embodiment of the present invention and its 3D printing preparation method into
Row illustrates.
A kind of 3D printing preparation method of titanium-based zirconium oxide composite material medical implant comprising:
By nanometer ZrO2Ceramic powder is mixed with default powder, obtains a nanometer ZrO2Powder coats the uniform multiple of default powder
Close powder；Wherein, powder and nanometer ZrO are preset2Ceramic powder mixes under energy oscillation, for breaking a nanometer ZrO2Ceramic powder
Van der Waals force between body；
3D printing is carried out after uniform composite powder is mixed with titanium alloy powder.
In detail, in an embodiment of the present invention, this method prints titanium-based zirconium oxide using titanium-based zirconium oxide composite material
Composite material medical implant, can have both excellent human compatibility and comprehensive mechanical property, and stock utilization is high.It is preparing
It is also added into default powder, such as nickel and cobalt in the process, preferably infiltration can be formed with zirconia ceramics and connect, can make
For transition metal, reduces the two and combine difficulty that it is higher with consistency that precision is prepared so that the utilization rate of material can be improved
Product.Meanwhile the elasticity modulus of human body bone is 35GPa, and the mechanical matching performance for the product being prepared by this method is
It is realized by the microstructure design of implant and the content of regulation nano zircite, therefore can ideally make up the prior art
Deficiency, by changing implant microstructure and nanometer ZrO2The system of the also customizable different mechanical properties of the content of ceramic powder
Part.
Further, in the preferred embodiment, presetting powder is nickel powder or cobalt powder；
And when default powder is nickel powder, uniform composite powder is nanometer ZrO2Powder coats the composite powder of nickel powder, when
When default powder is cobalt powder, uniform composite powder is nanometer ZrO2The composite powder of powder cladding cobalt powder.
In detail, in an embodiment of the present invention, nickel and cobalt are the formation elements of β phase titanium, can be infinitely dissolved with titanium, shape
At beta titanium alloy, and nickel or cobalt and ZrO2Ceramics all can also form preferably infiltration and connect, and titanium alloy and ceramics can be improved
Bonding strength.Certainly, in other embodiments of the invention, default powder can also can provide the powder of phase same-action for other
End, the embodiment of the present invention is without limitation.
Further, in the preferred embodiment, titanium alloy powder, nanometer ZrO2Ceramic powder and default powder
The mass percent at end is respectively 55~89%, 10~40%, 1~5%.
Further, in the preferred embodiment, the granularity of titanium alloy powder is 15~50 μm, nanometer ZrO2Pottery
The granularity of porcelain powder be 45~90nm, default powder granularity be 15~45 μm.Titanium alloy powder is to be with beta titanium alloy
It is main, when its granularity is at 15~50 μm, there are the characteristics such as human compatibility is good, density is low, intensity is high.Nanometer ZrO2Ceramic powder
It is containing rare earth oxide toughening TZP ceramics, when its powder granularity is between 45~90nm, human compatibility is good, wearability
Corrosion resistance is excellent.Certainly, in other embodiments of the invention, the size of each powder size can also carry out according to demand
Selection, the embodiment of the present invention is without limitation.
Further, in the preferred embodiment, nanometer ZrO2Ceramic powder and default powder are in ultrasonic energy
The lower mixing of oscillation, the uniform composite powder of formation are spherical cladding powder.The oscillation energy provided as needed is also possible to it
Its form, such as electromagnetic viscosimeter, the embodiment of the present invention is without limitation.
Further, in the preferred embodiment, 3D printing specifically includes:
Product threedimensional model is established, threedimensional model micro-structure is designed；
Every layer plane model is obtained with Slice Software；
Print every layer plane model from bottom to up in 3D printing equipment；
Product will be obtained after the accumulation of every layer plane model.
In detail, since human body flexible bone modulus is substantially in 35GPa or so, in the embodiment of the present invention, it can pass through
Change implant microstructure and nanometer ZrO2Ceramic powder content adjusts its mechanical property.
Further, in the preferred embodiment, the thickness of every layer plane model is 20~30 μm.Certainly,
In other embodiments of the invention, the thickness of every layer plane model can also be selected according to demand, implementation of the invention
Example is without limitation.
Further, in the preferred embodiment, to product in 850~950 DEG C of furnaces of Ar gas shielded and temperature
It is diffused annealing, 1.5~4h of time.
A kind of titanium-based zirconium oxide composite material medical implant is planted by above-mentioned titanium-based zirconium oxide composite material medical treatment
The 3D printing preparation method for entering body is prepared.The titanium-based zirconium oxide composite material medical implant is aoxidized by above-mentioned titanium-based
The 3D printing preparation method of zirconium composite material medical implant is prepared.Therefore, which plants
Precision and the consistency for entering body are high.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of titanium-based zirconium oxide composite material medical implant is present embodiments provided, is prepared by the following method
It arrives:
S1: taking mass percent is respectively 87%, 10%, 3% titanium alloy powder, nanometer ZrO2Ceramic powder, nickel powder,
Wherein, nanometer ZrO2Ceramic powder granularity is 45~90nm, and Ni alloy powder granularity is 15~45 μm, and titanium alloy powder granularity is
10~50 μm；
S2: by nanometer ZrO2Ceramic powder mixes in proportion with a small amount of nickel powder, is broken between nano powder with sonic oscillation method
Van der Waals force forms uniform composite powder；The composite powder is uniformly mixed in proportion with titanium base alloy powder again, merging 3D is beaten
It prints in operating room；
S3: establishing product threedimensional model, obtains each layer plane model using Slice Software, is 20 μm per thickness layer by layer；
S4: starting print routine, laser facula are completed first layer sectional view according to preset scan path and are printed, work
Make platform and decline 20 μm along Z axis, starts the second layering sectional view printing, repeat the process, constantly accumulation obtains product；
S5: the product printed is moved in heating furnace, there is Ar gas shield in furnace, and using annealing, temperature is
850 DEG C, time 1.5h completes the preparation of product.
Embodiment 2
A kind of titanium-based zirconium oxide composite material medical implant is present embodiments provided, is prepared by the following method
It arrives:
S1: taking mass percent is respectively 75%, 20%, 5% titanium alloy powder, nanometer ZrO2Ceramic powder, nickel powder,
Wherein, nanometer ZrO2Ceramic powder granularity is 45~90nm, and nickel powder granularity is 15~45 μm, and titanium alloy powder granularity is 15~50
μm；
S2: by nanometer ZrO2Ceramic powder mixes in proportion with nickel powder, breaks model moral between nano powder with sonic oscillation method
Hua Li forms uniform composite powder；The composite powder is uniformly mixed in proportion with base alloy powder again, merging 3D printing work
It is indoor；
S3: establishing product threedimensional model, obtains each layer plane model using Slice Software, is 25 μm per thickness layer by layer；
S4: starting print routine, laser facula are completed first layer sectional view according to preset scan path and are printed, work
Make platform and decline 25 μm along Z axis, starts the second layering sectional view printing, repeat the process, constantly accumulation obtains product；
S5: the product printed is moved in heating furnace, there is Ar gas shield in furnace, and using annealing, temperature is
900 DEG C, time 3h completes the preparation of product.
Embodiment 3
A kind of titanium-based zirconium oxide composite material medical implant is present embodiments provided, is prepared by the following method
It arrives:
S1: taking quality percentage is respectively 83%, 15%, 2% titanium alloy powder, nanometer ZrO2Ceramic powder, cobalt powder,
In, nanometer ZrO2Ceramic powder granularity is 45~90nm, and cobalt powder and titanium alloy powder granularity are 15~50 μm；
S2: by nanometer ZrO2Ceramic powder mixes in proportion with cobalt powder, breaks model moral between nano powder with sonic oscillation method
Hua Li forms uniform composite powder；The composite powder is uniformly mixed in proportion with titanium alloy powder again, merging 3D printing work
It is indoor；
S3: establishing product threedimensional model, obtains each layer plane model using Slice Software, is 30 μm per thickness layer by layer；
S4: starting print routine, laser facula are completed first layer sectional view according to preset scan path and are printed, work
Make platform and decline 30 μm along Z axis, starts the second layering sectional view printing, repeat the process, constantly accumulation obtains product；
S5: the product printed is moved in heating furnace, there is Ar gas shield in furnace, and using annealing, temperature is
950 DEG C, time 3h completes the preparation of product.
Comparative example 1
The hair of Publication No. CN105256160B entitled " 3D printing method of ceramic base nickel alloy composite material " a kind of
Bright patent application discloses a kind of using nickel alloy and ZrO2Printing prepares medical product, the side of use after ceramic powder mixing
Method is directly to mix two kinds of powder, and printing obtains nickel alloy ceramic composite product.
This method, the ZrO that will be mixed in proportion2.Ceramic powder and Ni base alloy powder are placed in metal 3D printing work
Make it is indoor, in 100~400W of power, 200~600mm/s of scanning speed, 30~60 μm of spot diameter, 40~70 μ of sweep span
It is printed under the conditions of m, operating room's oxygen concentration < 50ppm, the product that 3D printing is obtained is in N2At gas shielded and 800~890 DEG C of temperature
Annealing, 8~12h of time.The product material structure that the present invention prints is fine and close controllable, mechanical property adaptation, with excellent anti-corrosion
Performance, with short production cycle, low manufacture cost are adjustable at shape by changing ratio of the Ni60 alloy in basis material
The integral strength of part.
Comparative example 2
A kind of entitled " the 3D printing of ceramics titanium alloy composite material biology implantation product of Publication No. CN105728722A
The application for a patent for invention of method " is proposed titanium alloy powder and Al2O3、ZrO2Printing preparation biology implantation system after ceramics mixing
Part.But only there are two types of materials to mix for above-mentioned two pieces patent, and the method for preparing powder is mechanical mixture, it has not been found that 3D printing skill
Art coats zirconium oxide by nickel powder or cobalt powder, then is mixed with titanium-based zirconium oxide composite material titanium-based with three kinds of materials of Titanium Powder
The example of zirconium oxide composite material medical implant.
A kind of 3D printing method of ceramic titanium alloy composite material biology implantation product of this method: it will mix in proportion
Ceramic powder Zr02、A12O3Or ZrO2/A12O3Be placed in metal 3D printing operating room with titanium alloy powder, power 200~
500W, 200~600mm/s of scanning speed, 30~60 μm of spot diameter, 40~70 μm of sweep span, operating room's oxygen concentration <
It is printed under the conditions of 50ppm, the product that 3D printing is obtained carries out equal static pressure or solid at Ar gas shielded and 950~1050 DEG C of temperature
Molten processing, 1.5~4h of time.The product material that the present invention prints is good with human-body biological intermiscibility, and dense structure is poor, mechanical property
Can be bad, anti-corrosion wear resistance is preferable, by changing ratio of the titanium alloy in basis material, adjustable molded part
Integral strength.
Experimental example
Method that embodiment provides is compared with the method that comparative example provides it is found that the present invention and comparative example 1 and right
Ratio 2 compared to the advantages of be: directly print titanium-based zirconium oxide composite material medical implant using titanium-based zirconium oxide composite material,
Medical implant especially obtains uniform cladding powder under energy oscillation, can make printout by three kinds of material mixing
Ceramic phase is evenly distributed, and consistency is high, has both excellent human compatibility and comprehensive mechanical property, anti-corrosion abrasion resistance is good, can
It customizes, mechanical matching performance (human body flexible bone modulus 35GPa) can be by changing implant microstructure and nanometer ZrO2
The adjustment of ceramic powder content.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of 3D printing preparation method of titanium-based zirconium oxide composite material medical implant, characterized in that it comprises:
By nanometer ZrO2Ceramic powder is mixed with default powder, obtains a nanometer ZrO2Powder coats the uniform multiple of the default powder
Close powder；Wherein, the default powder and nanometer ZrO2Ceramic powder mixes under energy oscillation, for breaking the nanometer
ZrO2Van der Waals force between ceramic powder；
3D printing is carried out after the uniform composite powder is mixed with titanium alloy powder.
2. the 3D printing preparation method of titanium-based zirconium oxide composite material medical implant according to claim 1, feature
It is:
The default powder is nickel powder or cobalt powder；
And when the default powder is nickel powder, the uniform composite powder is nanometer ZrO2Powder coats the compound of the nickel powder
Powder, when the default powder is cobalt powder, the uniform composite powder is nanometer ZrO2Powder coats the compound of the cobalt powder
Powder.
3. the 3D printing preparation method of titanium-based zirconium oxide composite material medical implant according to claim 1, feature
It is:
The titanium alloy powder, the nanometer ZrO2The mass percent of ceramic powder and the default powder is respectively 55~
89%, 10~40%, 1~5%.
4. the 3D printing preparation method of titanium-based zirconium oxide composite material medical implant according to claim 1, feature
It is:
The granularity of the titanium alloy powder is 15~50 μm, the nanometer ZrO2The granularity of ceramic powder is 45~90nm, described
The granularity of default powder is 15~45 μm.
5. the 3D printing preparation method of titanium-based zirconium oxide composite material medical implant according to claim 1, feature
It is:
The nanometer ZrO2Ceramic powder includes rare earth oxide.
6. prepared by the 3D printing of titanium-based zirconium oxide composite material medical implant according to any one of claim 1 to 5
Method, it is characterised in that:
The nanometer ZrO2Ceramic powder and the default powder mix under ultrasonic energy oscillation, formation it is described uniformly compound
Powder is spherical cladding powder, the nanometer ZrO2Ceramic powder and the default powder can also apply condition in other energy
Lower mixing.
7. prepared by the 3D printing of titanium-based zirconium oxide composite material medical implant according to any one of claim 1 to 5
Method, which is characterized in that the 3D printing specifically includes:
Product threedimensional model is established, threedimensional model micro-structure is designed；
Every layer plane model is obtained with Slice Software；
Print every layer of areal model from bottom to up in 3D printing equipment；
The product will be obtained after every layer of areal model accumulation.
8. the 3D printing preparation method of titanium-based zirconium oxide composite material medical implant according to claim 7, feature
It is:
The thickness of every layer of areal model is 20~30 μm.
9. the 3D printing preparation method of titanium-based zirconium oxide composite material medical implant according to claim 7, feature
It is, further includes:
Annealing, 1.5~4h of time are diffused in 850~950 DEG C of furnaces of Ar gas shielded and temperature to the product.
10. a kind of titanium-based zirconium oxide composite material medical implant, it is characterised in that:
The titanium-based zirconium oxide composite material medical implant passes through titanium-based zirconium oxide described in any one of claims 1 to 9
The 3D printing preparation method of composite material medical implant is prepared.
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