CN114164366B - Tantalum-silver coating dental implant and preparation method thereof - Google Patents

Tantalum-silver coating dental implant and preparation method thereof Download PDF

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CN114164366B
CN114164366B CN202210120818.1A CN202210120818A CN114164366B CN 114164366 B CN114164366 B CN 114164366B CN 202210120818 A CN202210120818 A CN 202210120818A CN 114164366 B CN114164366 B CN 114164366B
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tantalum
silver
dental implant
base material
mass
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CN114164366A (en
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姜培齐
王路路
陈锡剑
宋国安
石培国
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Beijing Huatan Biotechnology Development Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/08—Artificial teeth; Making same
    • 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
    • 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
    • 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
    • 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
    • B33Y70/00—Materials specially adapted for 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
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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 tantalum-silver coating dental implant and a preparation method thereof, wherein the dental implant comprises a base material and a tantalum-silver coating, wherein the base material comprises, by mass, 0.5% -5% of titanium, 1% -5% of yttrium, 60% -80% of niobium, 5% -25% of zirconium and 3% -17% of silver; the raw materials of the tantalum-silver coating comprise, by mass, 94% -98% of tantalum, 0.5% -5% of silver, 0.2% -2% of magnesium and 0.2% -2% of strontium. The dental implant has the physical properties of high strength and low elastic modulus, and can effectively sterilize and resist corrosion and promote bone growth.

Description

Tantalum-silver coating dental implant and preparation method thereof
Technical Field
The invention belongs to the technical field of dental implantation, and particularly belongs to a tantalum-silver coating dental implant and a preparation method thereof.
Background
An artificial tooth is a bionic tooth made of biological material and is divided into a dental implant (tooth root) implanted in jaw bone and supporting and fixing the dental implant and a dental crown for chewing. A doctor selects a dental implant with a certain shape to be implanted into a jaw bone as an artificial tooth root according to the change of an alveolar bone and the jaw bone of a patient after losing teeth, and then installs a dental crown on an implantation pile exposed out of an oral cavity to obtain the shape and the function similar to those of a natural tooth.
The materials used by the existing dental implants on the market comprise ceramic materials, carbon materials, high polymer materials and metal materials, but the materials have various problems in clinical use, the ceramic materials belong to immediate gum-penetrating dental implants, the application range is narrow, the carbon materials have large brittleness, the black color of the carbon materials also limits the application range, the high polymer materials are easily degraded by organisms and stimulate human bodies, as for the metal materials, the metal materials used by the existing dental implants are mostly titanium metals and alloys thereof, and the materials have large hardness but the elastic modulus is far away from that of natural human bone tissues, so the materials have great constraint in use.
The conventional dental implant material generally has poor biocompatibility and is easy to cause peri-dental-implant mucositis and peri-dental-implant mucositis, and researches of scholars suggest that 79-90% of patients and 50% of dental implants have the risk of generating peri-dental-implant mucositis after the implant denture is repaired, and 28-56% of patients and 12-43% of implant sites have the risk of generating peri-dental-implant mucositis. Another study indicates that the incidence rate of peri-mucositis of dental implants is 60% -90%, and on the basis of such frequent inflammation, the development of a dental implant with a novel material and structure is urgently needed.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a tantalum-silver coating dental implant, which is characterized in that a tantalum-silver alloy coating is deposited on a titanium alloy base material, so that the advantages of low elastic modulus, good plasticity, high strength and the like of the original base material are kept, and the dental implant has the further advantages of good biocompatibility, antibiosis, corrosion resistance and the like.
The second purpose of the invention is to provide a preparation method of the tantalum-silver coating dental implant, the method comprises the steps of respectively preparing the base material and the coating, and then depositing through a PVD physical vapor deposition process to obtain the dental implant, wherein the preparation of the coating in the method adopts a fused deposition modeling technology to perform 3D printing, the printing precision is extremely high, and the printing requirement of the base material can be completed with half the effort.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention discloses a tantalum-silver coating dental implant, which comprises a base material and a tantalum-silver coating, wherein the base material comprises, by mass, 0.5% -5% of titanium, 1% -5% of yttrium, 60% -80% of niobium, 5% -25% of zirconium and 3% -17% of silver; the raw materials of the tantalum-silver coating comprise, by mass, 94% -98% of tantalum, 0.5% -5% of silver, 0.2% -2% of magnesium and 0.2% -2% of strontium.
Preferably, the base material comprises 1-3% of titanium, 2-4% of yttrium, 70-75% of niobium, 10-20% of zirconium and 5-15% of silver in percentage by mass; the raw materials of the tantalum-silver coating comprise, by mass, 95% -97% of tantalum, 1% -3% of silver, 0.5% -1.5% of magnesium and 0.5% -1.5% of strontium.
Preferably, the raw material of the base material comprises 1.1% of titanium, 3% of yttrium, 70.9% of niobium, 14.6% of zirconium and 10.4% of silver in percentage by mass; the raw materials of the tantalum-silver coating comprise, by mass, 96% of tantalum, 2% of silver, 1% of magnesium and 1% of strontium.
Among them, tantalum is the most important metal element in tantalum-silver coating, which is a valve metal, and it can generate a dense oxide film on the surface to have the property of unidirectional conductivity. The chemical property of the prepared oxide film is extremely stable, and the tantalum also has the advantages of wide working temperature range, high reliability, shock resistance, long service life and the like, and is an ideal material for manufacturing the capacitor with small volume and high reliability. Because of its many advantages, tantalum capacitors are widely used in electronic devices such as aviation, aerospace, communication, computer and mobile phones. In the present invention, the inventor has paid attention to the advantages of corrosion resistance, low elastic modulus, strong toughness, etc., and the dental implant material has the advantage of being remarkably thicker than the conventional dental implant material.
Silver is also one of important metal elements used in the invention, silver is one of trace elements of human body, the immunity of human body depends on silver to a great extent, and if the silver content in human body is lower than standard level, the possibility of bacterial infection is greatly improved.
Silver is a very safe element, and is accepted as the safest disinfectant; silver also has the effect of promoting tissue repair and regeneration. Throughout the world medicine, silver has a remarkable effect in the fields of gynecology, orthopedics, burn treatment, plastic face-lifting, nasopharyngitis treatment and the like.
The yttrium metal is used in a small amount in the invention, but plays a crucial role, is added into the existing alloy as a rare earth element, can effectively play a role in metamorphism, achieves the function of refining tissues, and can also remove impurities and gases, and the yttrium metal has a very low elastic modulus, and can also effectively reduce the elastic modulus of the base material and reduce the risk of breakage when added into the base material.
In a word, the tantalum-silver coating is added on the base material, so that the risk of periodontal infection is reduced, the antibacterial property is improved, the cell growth of periodontal is promoted, and in addition, after the formula of the original base material is properly improved, the base material and the tantalum-silver coating can be better fused with each other, so that the excellent effects of improving the comfort degree of the dental implant and improving the antibacterial property are achieved.
Preferably, the tantalum-silver coating thickness of the dental implant of the present invention is 100nm to 1500 nm.
Preferably, the area of the substrate on which the biomimetic bone trabecular structure is provided is between 20% and 40% of the surface area of the substrate.
Preferably, the length of the base material is 6.5mm to 16.0mm, and the diameter of the neck portion is 3.5mm to 6.0 mm.
Preferably, the thread pitch of the double thread is 1.1mm-1.3mm, and the lead is 2.2mm-2.6 mm.
Preferably, the substrate is provided with a bionic bone trabecula structure, the bionic bone trabecula is a curved surface porous structure, the porosity of the bionic bone trabecula structure is 15% -85%, the size of the pore diameter is 0.1mm-1mm, the average silk diameter is 180 μm-780 μm, and the pore structure on the bionic bone trabecula structure comprises a regular hexahedron, a face-centered cube, a rotating face-centered cube and a rhombic dodecahedron structure.
Preferably, the bionic bone trabecula structure is arranged in the middle of the base material, and the top and the bottom of the base material are both compact structures without holes; the base material is provided with a double-thread structure, and the bionic bone trabecula structure is arranged on the thread crest of the double threads and extends to the thread crest.
Preferably, the substrate comprises a neck and a body, the bionic bone trabecular structure is located in the middle of the body and is located close to the neck, and the top and the bottom of the neck and the body are compact structures.
The neck is cylindrical, the somatic part is round platform shape, the main aspects of somatic part with the neck is connected, along keeping away from the neck direction the diameter of somatic part evenly reduces.
In a word, the structure of the bionic bone trabecula on the base material is diversified, and various hole structures are brought by the diversified structure of the bionic bone trabecula, so that a better bionic effect can be achieved, the dental implant can be better compatible with a human body, the growth of bones is promoted, and the effect of quickly bearing load is achieved.
In addition, for a specific bionic bone trabecular structure, parameters such as specific porosity, pore size and wire diameter are specially limited, because tests show that the porosity is too large or too small, the pore size is too large or too small, and the size of the wire diameter is too large or too small, which affects the specific growth condition of the dental implant, because if the pore size is too small or the porosity is too small, which affects the growth condition of the bone, the bone growth is less, and the bonding strength is affected, if the pore size is too large or the porosity is too large, although the bone grows, the strength of the whole dental implant is affected, so when the parameters are set, the growth performance of the bone is considered, and the bonding strength and the strength of the whole dental implant are considered at the same time.
The invention provides a novel dental implant structure and a preparation method of the dental implant, and the preparation method specifically comprises the following steps:
preparing titanium, yttrium, niobium, zirconium and silver into composite powder according to a proportion, and performing layer-by-layer stacking molding by using a fused deposition molding technology;
machining to obtain the base material, wherein a bionic bone trabecula structure is arranged on the base material;
and depositing the target material to the base material by using a PVD physical vapor deposition process to obtain the tantalum-silver coating, thus obtaining the dental implant.
Wherein the PVD physical vapor deposition process comprises the steps of:
ionizing argon gas under a vacuum condition to generate argon ions;
the argon ions bombard the target material at high speed under the action of an electric field;
the sputtered target atoms or atomic groups migrate to the surface of the substrate and deposit to form a coating.
Preferably, the fused deposition modeling method comprises the following steps:
constructing a three-dimensional model of the dental implant;
and according to the three-dimensional model, using the composite powder as a raw material to perform additive manufacturing.
Preferably, the fused deposition modeling technique is one of a laser melting technique or an electron beam melting technique, and may be other fused deposition modeling techniques. Wherein the laser melting technical parameters comprise:
the laser power is 130W-350W, preferably 180W-260W; the scanning speed is 80mm/s-400mm/s, preferably 120mm/s-330 mm/s; the distance between the scanning lines is 0.03mm-0.15mm, preferably 0.06mm-0.09 mm; the slice layer thickness is 15 μm to 60 μm, preferably 30 μm to 40 μm; the temperature of the substrate is 50-250 ℃, preferably 130-180 ℃;
wherein the electron beam melting technical parameters comprise:
the preheating temperature of the powder is 800-1600 ℃, and the preferred preheating temperature is 1000-1400 ℃; scanning currentIs 3mA-20mA, preferably 6mA-12 mA; the scanning speed is 0.8 × 104mm/s-9.0×105mm/s, preferably 2.0X 104mm/s-7.0×105mm/s; the slice layer has a thickness of 15 μm to 60 μm, preferably 30 μm to 40 μm.
Preferably, the preparation method of the target material used in the scheme of the invention comprises the following steps:
respectively preparing tantalum, silver, magnesium and strontium into powder with the particle size of less than 10 mu m, and uniformly mixing the powder according to the proportion to obtain mixed powder;
cold isostatic pressing the mixed powder;
and cutting a product prepared by cold isostatic pressing to obtain the target.
The cold isostatic pressing comprises the following steps:
placing the mixed powder in a hydraulic machine for cold isostatic pressing to prepare a primary material, wherein the pressure of the cold isostatic pressing is 90-150 MPa, and the static pressing time is 10-20 min;
crushing the primary material and sieving the crushed primary material by a sieve of 80 meshes to 120 meshes;
and carrying out cold isostatic pressing and then carrying out heat preservation sintering at the temperature of 1300-1400 ℃ for 30-80 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) the base material is made of a flexible material with low elastic modulus, has high strength and high metal flexibility, reduces the risk of breaking, and has extremely high plasticity.
(2) 3D printing is carried out by adopting a fused deposition modeling technology, so that the precision is high and the cost is low.
(3) The bionic bone trabecula structure is exquisite in design, can effectively simulate the real bone trabecula structure, and promotes the growth of bones.
(4) The coating is made of tantalum-silver alloy and has excellent antibacterial and corrosion-resistant effects.
(5) The product has no cytotoxicity and tissue rejection through biological detection of Chinese academy of sciences.
(6) The binding force of the coating is superior to the tensile strength of the conventional hydroxyapatite coating, and the tensile shear strength of the coating of the product is more than 30 MPa.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic view of a dental implant according to an embodiment of the present invention; in fig. 1, 1 is a bionic bone trabecular structure;
FIG. 2 is an electron diffraction pattern of a coating provided by an embodiment of the present invention;
FIG. 3 is an electron microscope image of a dental implant according to an embodiment of the present invention;
FIG. 4 is a moire pattern of a coating provided by an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Example 1
Referring to fig. 1-4, fig. 1 is a schematic structural view of a dental implant, fig. 2 is an electron diffraction pattern of a coating provided by an embodiment of the present invention, fig. 3 is an electron microscope image of a dental implant provided by an embodiment of the present invention, and fig. 4 is a moire fringe pattern of a coating provided by an embodiment of the present invention. The polycrystalline structure and the moir e pattern of the coating are clearly visible in the figure, and the coating region in the middle and the substrate region at the bottom are also clearly discernible in figure 3.
The preparation method of the tantalum-silver coating dental implant provided by the embodiment comprises the following steps:
mixing metal powder of titanium, yttrium, niobium, zirconium and silver according to the mass percentage of 1.1%, 3%, 70.9%, 14.6% and 10.4% to obtain composite powder, and performing 3D printing on the composite powder by using a fused deposition modeling technology, wherein a laser melting technology is used in the embodiment;
wherein the parameters in the laser melting technical process comprise: the laser power is 200W, the scanning speed is 250mm/s, the scanning line spacing is 0.08mm, the slicing layer thickness is 35 μm, and the substrate temperature is 150 ℃.
The implant substrate structure can be obtained after a product prepared by a fused deposition modeling technology is machined and molded, a curved surface porous bionic bone trabecula structure is arranged in the middle of the substrate, the substrate is provided with a double-thread structure, the bionic bone trabecula structure is arranged on the thread crest of the double threads and extends to the thread crest, the bionic bone trabecula structure is only arranged in the middle of the substrate, and the top and the bottom of the substrate are compact structures.
The porosity of the bionic bone trabecular structure is 15% -85%, and in the embodiment, the porosity is 60%;
the aperture size of the bionic bone trabecula structure is 0.1mm-1mm, and the aperture size in the embodiment is 0.5 mm;
the average silk diameter of the bionic bone trabecular structure is 180-780 mu m, and in the embodiment, the average silk diameter is 480 mu m;
the pore canal connectivity of the bionic bone trabecular structure is more than 90 percent, and in the embodiment, the connectivity is 95 percent;
the pore structure on the bionic bone trabecula structure comprises a regular hexahedron, a face-center cube, a rotary face-center cube and a rhombic dodecahedron structure, and the pore structure is a regular hexahedron in the embodiment.
Tantalum, silver, magnesium and strontium are respectively prepared into powder with the particle size of below 10 microns, the particle size of the powder in the embodiment is 5 microns, and the powder is uniformly mixed according to the mass percentage of 96%, 2%, 1% and 1% to obtain mixed powder;
carrying out cold isostatic pressing and cutting on the mixed powder to obtain a target material;
and depositing the target material to the base material by using a PVD physical vapor deposition process to obtain the tantalum-silver coating, thus obtaining the dental implant.
The PVD physical vapor deposition process comprises the following steps:
ionizing argon gas under a vacuum condition to generate argon ions;
the argon ions bombard the target material at high speed under the action of an electric field;
the sputtered target atoms or atomic groups migrate to the surface of the substrate and deposit to form a coating.
The cold isostatic pressing comprises the following steps:
placing the mixed powder in a hydraulic machine for cold isostatic pressing to prepare a primary material, wherein the pressure of the cold isostatic pressing is 90MPa-150MPa, the time of the cold isostatic pressing is 10min-20min, and the pressure of the cold isostatic pressing is 120MPa for 15min in the embodiment;
crushing the primary material and sieving the crushed primary material by a sieve of 80 meshes to 120 meshes, in this embodiment, sieving the crushed primary material by a sieve of 100 meshes;
and carrying out cold isostatic pressing and then carrying out heat preservation sintering at the temperature of 1300-1700 ℃, wherein the sintering time is 30-80 h, the temperature in the embodiment is 1500 ℃, and the sintering time is 50 h.
Example 2
The specific procedure was identical to that of example 1, except that the metal powders of titanium, yttrium, niobium, zirconium and silver were present in percentages by mass of 0.5%, 5%, 60%, 25% and 3%;
the mass percentages of tantalum, silver, magnesium and strontium are 94%, 5%, 0.2% and 2%;
wherein the parameters in the laser melting technical process comprise: the laser power is 130W, the scanning speed is 80mm/s, the scanning line spacing is 0.03mm, the slicing layer thickness is 15 mu m, and the substrate temperature is 50 ℃;
the porosity of the bionic bone trabecular structure is 15%;
the aperture size of the bionic bone trabecula structure is 0.1 mm;
the average silk diameter of the bionic bone trabecular structure is 180 mu m;
the pore structure on the bionic bone trabecula structure is a face-centered cube.
Example 3
The specific procedure was identical to that of example 1, except that the metal powders of titanium, yttrium, niobium, zirconium and silver were 5%, 1%, 80%, 5% and 17% by mass;
the mass percentages of tantalum, silver, magnesium and strontium are 98%, 0.5%, 2% and 0.2%;
wherein the parameters in the laser melting technical process comprise: the laser power is 350W, the scanning speed is 400mm/s, the scanning line spacing is 0.15mm, the slicing layer thickness is 60 mu m, and the substrate temperature is 250 ℃;
the porosity of the bionic bone trabecular structure is 85%;
the aperture size of the bionic bone trabecula structure is 1 mm;
the average silk diameter of the bionic bone trabecular structure is 780 mu m;
the pore structure on the bionic bone trabecula structure is a rotating face-centered cube.
Example 4
The specific procedure was identical to that of example 1, except that the metal powders of titanium, yttrium, niobium, zirconium and silver were present in percentages by mass of 1%, 4%, 70%, 20% and 5%;
the mass percentages of tantalum, silver, magnesium and strontium are 95%, 3%, 0.5% and 1.5%;
in this embodiment, the fused deposition is performed by using an electron beam melting technique, and the parameters of the electron beam melting include: the preheating temperature of the powder is 800 ℃, the scanning current is 3mA, and the scanning speed is 0.8 multiplied by 104mm/s, the slice layer thickness is 15 μm;
the pore structure on the bionic bone trabecula structure is a rhombic dodecahedron structure.
Example 5
The specific procedure was identical to that of example 1, except that the metal powders of titanium, yttrium, niobium, zirconium and silver were present in percentages by mass of 3%, 2%, 75%, 10% and 15%;
the mass percentages of tantalum, silver, magnesium and strontium are 97%, 1%, 1.5% and 0.5%;
in this embodiment, the fused deposition is performed by using an electron beam melting technique, and the parameters of the electron beam melting include: the preheating temperature of the powder is 1600 ℃, the scanning current is 20mA, and the scanning speed is 9.0 multiplied by 105mm/s, slice layer thickness 60 μm.
Example 6
The specific procedure was identical to example 1, except that the porosity of the biomimetic bone trabecular structure was 70%.
Example 7
The specific procedure was identical to example 1, except that the metal powders of titanium, yttrium, niobium, zirconium and silver were present in percentages by mass of 1.1%, 5%, 68.9%, 14.6% and 10.4%;
the mass percentages of tantalum, silver, magnesium and strontium are 96%, 2%, 1% and 1%.
Example 8
The specific procedure was identical to example 1, except that the metal powders of titanium, yttrium, niobium, zirconium and silver were present in percentages by mass of 1.1%, 3%, 70.9%, 14.6% and 10.4%;
the mass percentages of tantalum, silver, magnesium and strontium are 97.5%, 0.5%, 1% and 1%.
Example 9
The specific procedure is identical to example 1, except that the porosity of the biomimetic bone trabecular structure is 90%.
Example 10
The specific procedure was identical to example 1, except that the pore size of the biomimetic bone trabecular structure was 1.2 mm.
Example 11
The procedure was as in example 1 except that the average filament diameter of the biomimetic bone trabecular structure was 100. mu.m.
Comparative example 1
The procedure was as in example 1 except that the yttrium content in the base material was 0.5% and the silver content was 12.9%.
Comparative example 2
The specific procedure is the same as in example 1 except that the coating is a conventional hydroxyapatite coating.
Comparative example 3
The specific operation steps are the same as those of example 1, except that the raw materials of the coating, namely tantalum, silver, magnesium and strontium, comprise the following components in percentage by mass: 87%, 7%, 3% and 3%.
Experimental example 1
The dental implants of examples 1 to 11 and comparative examples 1 to 3 were subjected to antibacterial tests, and the evaluation methods of the tests were as follows:
staphylococcus aureus was tested according to the method in the national Standard "food microbiology test Staphylococcus aureus test" (GB 4789.10-2016).
Escherichia coli was examined according to the method in the national Standard food safety food microbiology examination coliform population (GB 4789.3-2010).
The test data are shown in table 1 below:
TABLE 1 results of the antibacterial ratio measurements
Group of Antibacterial rate of staphylococcus aureus Antibacterial rate of Escherichia coli
Example 1 100％ 100％
Example 2 100％ 100％
Example 3 100％ 100％
Example 4 100％ 100％
Example 5 100％ 100％
Example 6 100％ 100％
Example 7 100％ 100％
Example 8 100％ 100％
Example 9 100％ 100％
Example 10 100％ 100％
Example 11 100％ 100％
Comparative example 1 85％ 79％
Comparative example 2 54％ 32％
Comparative example 3 68％ 76％
Experimental example 2
The dental implants of examples 1-11 and comparative examples 1-3 were subjected to cytotoxicity tests, and the evaluation methods of the tests were as follows:
preparing a leaching solution by using a serum-containing cell culture solution, and performing biological evaluation on medical instruments according to the national standard GB/T16886.5-2017 part 5: in vitro cytotoxicity assay the in vitro cytotoxicity assay was carried out according to the method recommended in vitro cytotoxicity assay.
And (3) contacting a proper test sample leaching liquor with cultured cells, respectively contacting corresponding blank control liquor, negative control leaching liquor and positive control leaching liquor with the cultured cells, measuring the absorbance value of each group after 24 hours, and calculating the cell survival rate of the test sample. The test results are shown in table 2 below:
TABLE 2 cell viability assay results
Group of Absorbance of the solution Survival rate
Example 1 0.637 121％
Example 2 0.630 120％
Example 3 0.632 111％
Example 4 0.584 114％
Example 5 0.627 119％
Example 6 0.630 120％
Example 7 0.634 115％
Example 8 0.633 114％
Example 9 0.635 114％
Example 10 0.634 113％
Example 11 0.634 112％
Comparative example 1 0.632 115％
Comparative example 2 0.590 101％
Comparative example 3 0.629 106％
Experimental example 3
The dental implants of examples 1 to 11 and comparative examples 1 to 3 were subjected to mechanical tests, and the evaluation methods of the tests were as follows:
the dental implants of examples 1 to 11 and comparative examples 1 to 3 were mixed with an equal volume of glyceryl monostearate powder, heated and melted, and the biomechanical properties thereof were measured using a constant-wing instrument biomechanical tester, and the prepared samples were directly immersed in warm water for 12 hours and 3 days, and then taken out and dried for 3 hours, and the measurement data are shown in the following tables 3.1 and 3.2:
TABLE 3.1 biomechanical test results of 12h immersion
Group of Best force (N) Maximum deformation (mm) Appearance of the product
Example 1 12.5 6.0 No crack and high hardness
Example 2 11.1 6.0 No crack and high hardness
Example 3 11.5 6.0 No crack and high hardness
Example 4 12.1 6.0 No crack and high hardness
Example 5 12.1 6.0 No crack and high hardness
Example 6 12.4 6.0 No crack and high hardness
Example 7 12.2 6.0 No crack and high hardness
Example 8 11.8 6.0 No crack and high hardness
Example 9 10.9 6.0 No crack and high hardness
Example 10 11.1 6.0 No crack and high hardness
Example 11 11.3 6.0 No crack and high hardness
Comparative example 1 8.6 4.0 Cracked and crisp
Comparative example 2 9.5 4.0 Cracked and crisp
ComparisonExample 3 10.6 5.0 No crack and high hardness
TABLE 3.2 biomechanical test results of 3d soak
Figure GDA0003550981460000131
Figure GDA0003550981460000141
Experimental example 4
The dental implants of examples 1 to 11 and comparative examples 1 to 3 were subjected to in vivo growth experiments, and the evaluation methods of the experiments were as follows: the bone ingrowth effect and alveolar defect restoration effect were measured by a large animal test, and the dental implants of examples 1 to 11 of the present invention and comparative examples 1 to 3 were implanted in the oral cavity of an adult beagle dog as a test animal model.
The implantation operation comprises the following steps: firstly, preparing a dentition defect model, implanting the right mandible, binding the lateral clinostatism position of a dog on an operating table after anesthesia, separating gum by a gum stripper, using an ultrasonic osteotome to match with a dental elevator and dental forceps, extracting left and right mandible teeth, taking out residual tooth fragments and alveolar bone fragments in an alveolar pit, polishing the alveolar bone to be flat and smooth, flushing the operation area by using physiological saline, and suturing and closing the wound. The conventional implantation after 90d healing of the alveolar bone comprises the following steps: and (3) making a 4cm incision in the center of the alveolar ridge crest by using a sharp knife until the alveolar ridge crest is reached, turning up the whole posterior valve of the mucoperiosteum and exposing the alveolar bone. And removing the granulation tissue on the surface of the tooth extraction wound by using a scaling device, and polishing and flattening the alveolar bone tip by using a slow speed ball drill. Preparing a planting pit, and implanting the dental implant to enable the top end of the dental implant to be level with the crest of the alveolar ridge and be slightly lower after the dental implant is implanted. The gingival tissue is repositioned and the wound is closed by suturing. The test animals were housed in a conventional high protein diet after surgery. And (4) obtaining the lower jaw bone at 28d and 84d time points after the implantation, detecting the bonding strength of the implanted sample and the surrounding tissues by adopting an axial stress pushing method, carrying out Micro-CT scanning, and qualitatively and quantitatively evaluating the bone ingrowth effect. The change of the condition of inflammation, new bone tissue growth, osseointegration rate and the like of the mandible is observed by the histopathology.
The results of large animal experiments show that the bonding strength between the tantalum-silver coating dental implant provided by the embodiments 1-11 and the surrounding bone tissue after the operation of 28d is greater than 20 MPa; after operation 84d, the scan shows that the new bone in the test group completely fills the cavity, the bone growth volume ratio is higher than 60%, and no histopathological change is visible at the joint of the dental implant and the mandible, particularly, the effect of the example 1 is most remarkable, the effect of the bone growth in the example 11 is not as good as that of other examples because the wire diameter of the bionic bone trabecular structure is smaller than the set value, and the experimental data of the comparative examples 1-3 do not reach the data standard of the examples.
Experimental example 5
The dental implants of examples 1-11 and comparative examples 1-3 were subjected to bone implantation experiments, according to the following specific experimental protocol: each new zealand rabbit was anesthetized using a sutai ear injection. Penicillin and streptomycin were intramuscular injected before surgery. Removing the periderm in the operation area, and disinfecting the operation position by iodophor and alcohol; and (5) conventionally paving the towel. The surgery is performed under sterile conditions. Cutting the skin of the condyle of femur of a rabbit; muscle, myofascial was isolated. Drilling a cavity on the outer side of the left femoral condyle intermittently at a low speed by using an electric drill to remove bone fragments; the dental implants of examples 1 to 11 and comparative examples 1 to 3 were each implanted in a plug-in manner such that the surface of the sample was flush with or slightly lower than the surface of cortical bone, followed by suturing myofascial and skin incision, and then were housed in the center of the animal after surgery. Each new zealand rabbit was sacrificed by carbon dioxide humane at 1 week, 4 weeks, 12 weeks, 26 weeks time points. The entire femoral condyle was cut with a saw. After being treated by neutral formaldehyde bone nail and properly decalcified, the bone nail is treated conventionally and observed histologically under the microscope.
The bone implantation experiment of experimental example 5 shows that the tantalum-silver coated dental implant of the present invention is non-irritant under the above experimental conditions in both the examples 1-11 and the comparative examples 1-3.
It is apparent from the above experimental examples 1-5 that example 1 is the best example provided by the present invention, and it is excellent in antibacterial property experiment, cytotoxicity experiment, mechanical experiment, in vivo growth experiment, and bone implantation experiment, and the data of examples 1-11 are the data of comparative examples 1-3, so that it can be seen that the parameters provided by the present invention are the most reasonable design.
Particularly, in the antibacterial property experiment of the experimental example 1, it can be obviously seen that the antibacterial property of the coating of the invention is remarkably reduced in the comparative example 2 because the coating is not selected, which shows that the tantalum-silver coating of the invention can effectively play an antibacterial effect; in addition, in the comparative example 1, the addition amount of yttrium in the base material is reduced, and the addition amount of the raw material of silver is increased, but the experimental result shows that the antibacterial performance of the comparative example 1 is reduced, which indicates that the addition of yttrium in the base material is not only simple for reducing the elastic modulus of the material, but also can generate a compounding effect with silver in the base material to enhance the antibacterial performance of the silver, and once the proportion is not suitable, the antibacterial performance is naturally reduced.
The cytotoxicity test of experimental example 2 and the bone implant test of experimental example 5 are to show that the product of the present invention is not cytotoxic and is non-irritating to the living body.
In the mechanical experiment of experiment example 3, it can be seen that the strength of the physical layer of comparative example 1 and comparative example 2 is not related due to the fact that the addition amount of yttrium is not small or the coating of the present invention is not used, while in examples 9-11, the data result of designing the porosity, pore size and average wire diameter of the bionic bone trabecular structure is not as good as that of example 1, and the problem of bone growth and the problem of strength of the whole dental implant can be simultaneously taken care of only within the range specified by the present invention.
Experimental example 4 biological in vivo experiments also show that the design of the invention can effectively promote bone growth.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (12)

1. The tantalum-silver coated dental implant is characterized by comprising a base material and a tantalum-silver coating deposited on the base material, wherein the base material comprises 0.5-5% of titanium, 1-5% of yttrium, 60-80% of niobium, 5-25% of zirconium and 3-17% of silver in percentage by mass; the raw materials of the tantalum-silver coating comprise, by mass, 94% -98% of tantalum, 0.5% -5% of silver, 0.2% -2% of magnesium and 0.2% -2% of strontium.
2. The tantalum-silver coated dental implant of claim 1, wherein the raw material of the base material comprises, by mass, 1% -3% of titanium, 2% -4% of yttrium, 70% -75% of niobium, 10% -20% of zirconium and 5% -15% of silver; the raw material of the tantalum-silver coating comprises, by mass, 95% -97% of tantalum, 1% -3% of silver, 0.5% -1.5% of magnesium and 0.5% -1.5% of strontium.
3. The tantalum-silver coated dental implant of claim 1, wherein the base material comprises, in mass%, 1.1% of titanium, 3% of yttrium, 70.9% of niobium, 14.6% of zirconium and 10.4% of silver; the raw materials of the tantalum-silver coating comprise, by mass, 96% of tantalum, 2% of silver, 1% of magnesium and 1% of strontium.
4. The tantalum-silver coated dental implant of any one of claims 1 to 3, wherein the substrate is provided with a curved porous biomimetic bone trabecular structure;
the pore canal connectivity of the bionic bone trabecula structure is more than 90 percent;
the pore structure on the bionic bone trabecula structure comprises a regular hexahedron, a face-center cube, a rotary face-center cube and a rhombic dodecahedron structure.
5. The tantalum-silver coated dental implant of claim 4, wherein the biomimetic bone trabecular structure has a porosity of 15% -85%.
6. The tantalum-silver coated dental implant of claim 4, wherein the pore size of the biomimetic bone trabecular structure is in the range of 0.1mm to 1 mm.
7. The tantalum-silver coated dental implant of claim 4, wherein the biomimetic bone trabecular structure has an average filament diameter of 180 μm to 780 μm.
8. The tantalum-silver coated dental implant of claim 4, wherein the biomimetic bone trabecular structure is disposed in the middle of the substrate, the top and bottom of the substrate are dense structures, and the biomimetic bone trabecular structure is absent; the base material is provided with a double-thread structure, and the bionic bone trabecula structure is arranged on the thread crest of the double threads and extends to the thread crest.
9. The method for preparing a dental implant according to any one of claims 1 to 8, comprising the steps of:
preparing titanium, yttrium, niobium, zirconium and silver into composite powder according to a proportion, and performing layer-by-layer stacking molding by using a fused deposition molding technology;
machining to obtain the base material, wherein a bionic bone trabecula structure is arranged on the base material;
and depositing a target material on the surface of the substrate by using a PVD physical vapor deposition process to form the tantalum-silver coating.
10. The method of claim 9, wherein the fused deposition modeling technique comprises the steps of:
constructing a three-dimensional model of the implant;
according to the three-dimensional model, using the composite powder as a raw material to perform additive manufacturing;
the fused deposition modeling technology is one of a laser melting technology or an electron beam melting technology, wherein the parameters of the laser melting technology comprise:
the laser power is 130W-350W, the scanning speed is 80mm/s-400mm/s, the scanning line spacing is 0.03mm-0.15mm, the slicing layer thickness is 15 mu m-60 mu m, and the substrate temperature is 50 ℃ to 250 ℃;
wherein the electron beam melting technical parameters comprise:
the preheating temperature of the powder is 800-1600 ℃, the scanning current is 3-20 mA, and the scanning speed is 0.8 multiplied by 104mm/s-9.0×105mm/s, the slice layer thickness is 15 μm-60 μm.
11. The method according to claim 9, wherein the method comprises the steps of:
preparing tantalum, silver, magnesium and strontium into powder with the particle size of below 10 mu m;
mixing, cold isostatic pressing and cutting to obtain the target material with uniform components and high purity.
12. Preparation method according to claim 9, characterized in that the PVD process comprises the following steps:
ionizing argon gas under a vacuum condition to generate argon ions;
the argon ions bombard the target material at high speed under the action of an electric field;
the sputtered target atoms or atomic groups migrate to the surface of the substrate and deposit to form a coating.
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