CN209292473U - Titanium alloy composite material, surgical implant and medical instrument - Google Patents
Titanium alloy composite material, surgical implant and medical instrument Download PDFInfo
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- CN209292473U CN209292473U CN201822129956.8U CN201822129956U CN209292473U CN 209292473 U CN209292473 U CN 209292473U CN 201822129956 U CN201822129956 U CN 201822129956U CN 209292473 U CN209292473 U CN 209292473U
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Abstract
The utility model provides a kind of titanium alloy composite material, surgical implant and medical instrument, is related to titanium alloy composite material technical field.The titanium alloy composite material includes titanium alloy substrate and the diamond coatings for being formed in titanium alloy-based bottom surface, diamond coatings include micron diamond and nano-diamond layer, micron diamond is in the discontinuous distribution of titanium alloy-based bottom surface, nano-diamond layer is formed in the surface and micron diamond surface that micron diamond is not distributed with for titanium alloy substrate, the diamond coatings have certain bactericidal bacteriostasis, there are stable physicochemical properties simultaneously, and lower coefficient of friction, higher hardness and elastic modulus, so that the titanium alloy composite material that the diamond coatings and titanium alloy substrate are compounded to form has excellent biocompatibility, bactericidal effectiveness and corrosion-resistant and abrasion resistance properties.The utility model additionally provides a kind of surgical implant and medical instrument, with good medical application prospect.
Description
Technical field
The utility model relates to titanium alloy composite material technical field, in particular to a kind of titanium alloy composite material,
Surgical implant and medical instrument.
Background technique
Titanium alloy is a kind of 20th century important alloy material for growing up of mid-term.It is just opened from titanium alloy the 1960s
Begin extensively in the development and application of biomedical devices field, application field relates generally to more such as orthopaedics, orthopaedic srugery, cardiovascular and cerebrovascular
Section.Especially as main implantation material for surgery, titanium alloy tool has various advantages compared with other materials.For example, titanium closes
The biocompatibility and corrosion resistance and good of gold, titanium alloy, which is implanted into fluid environment, will form fine and close oxide layer, the oxide layer
Chemical inertness is high, and bio-toxicity is low, and the probability of adsorbed protein molecules is also smaller, thus tissue rejection is low, has good
Biocompatibility.On the other hand, titanium alloy has better toughness compared with other metals such as stainless steel, can be different according to partes corporis humani position
Anatomic form complete implants moulding, preferably performance physiological function.
Due to implantation material for surgery or medical instrument and human contact, intervene or implant after influence to host be
One extremely complex process may cause all including tissue reaction, reaction of blood, immune response and general reaction
More biological modifications, to such as infection, calcification, thromboembolism, tumour complication occur.It is also deposited as titanium alloy implantation material
In certain defect, i.e. surface bioactive is not high, also, titanium alloy is after being implanted into human body, due to titanium alloy wearability and anti-corruption
Corrosion is poor, and in human physiological environment especially in needing load bearing position, serious corrosion, cell adaptation is bright
Aobvious to reduce, the micro harmful metal ion such as vanadium and aluminium is easy to be released in human body human body, can do harm to huamn body.
Titanium alloy itself does not have anti-microbial property simultaneously, easily causes the bacterium infection of ambient enviroment and then leads to operative failure and morbidity
Rate increases.
In view of this, special propose the utility model at least one of to solve the above technical problems.
Utility model content
First of the utility model is designed to provide a kind of titanium alloy composite material, by setting in titanium alloy substrate
The diamond coatings of specific structure are set, so that the titanium alloy composite material has good anti-microbial property, corrosion-resistant and wear-resistant
Performance.
Second of the utility model is designed to provide a kind of surgical implant, including above-mentioned titanium alloy composite material.
The third of the utility model is designed to provide a kind of medical instrument, including above-mentioned titanium alloy composite material or outer
Surgical implant.
In order to realize the above-mentioned purpose of the utility model, the following technical scheme is adopted:
The utility model provides a kind of titanium alloy composite material, comprising:
Titanium alloy substrate and the diamond coatings for being formed in the titanium alloy-based bottom surface；
Wherein, the diamond coatings include being located at the micron diamond island on the same surface of the titanium alloy substrate and receiving
Rice diamond layer；
The micron diamond island is discontinuous to be set to the titanium alloy-based bottom surface；
The nano-diamond layer is set to micron diamond island surface and the titanium alloy substrate is not provided with
The surface on the micron diamond island.
Further, on the basis of technical solutions of the utility model, the partial size on the micron diamond island is 2~5 μ
m。
Further, on the basis of technical solutions of the utility model, the micron diamond island is single micron chickens
Hard rock particle；And/or
The micron diamond island is the aggregation that multiple Nano diamond particles are formed.
Further, on the basis of technical solutions of the utility model, between the adjacent micron diamond island
Distance is less than 2 μm.Further, on the basis of technical solutions of the utility model, the thickness of the nano diamond coating
For 50~200nm.
Further, on the basis of technical solutions of the utility model, nanometer Buddha's warrior attendant in the nano diamond coating
The partial size of stone is 3~20nm.
Further, on the basis of technical solutions of the utility model, the titanium alloy substrate is the conjunction of Ti-6Al-4V titanium
Any one in gold substrate, Ti-5Al-2.5Sn titanium alloy substrate or Ti-12Mo-6Zr-2Fe titanium alloy substrate.
The utility model additionally provides a kind of surgical implant, including above-mentioned titanium alloy composite material.
Further, on the basis of technical solutions of the utility model, the surgical implant include wire for correcting shape of tooth,
Root canal file, spinal column correction bar, bone plate, intramedullary needle, patella claw, seal wire, guide pin, cardiac patch, intravascular stent, thrombus filter,
Appointing in esophageal stents, respiratory tract bracket, biliary tract rack, urethra rack, rectum bracket, duodenal stent or external auditory canal bracket
It anticipates one kind.
The utility model additionally provides a kind of medical instrument, including above-mentioned titanium alloy composite material or above-mentioned surgical implantation
Object.
Compared with prior art, titanium alloy composite material provided by the utility model, surgical implant and medical instrument tool
Have it is following the utility model has the advantages that
(1) the utility model provides a kind of titanium alloy composite material, including titanium alloy substrate and is formed in titanium alloy-based
The diamond coatings of bottom surface, the diamond coatings include micron diamond island and nano-diamond layer, wherein micron Buddha's warrior attendant
Stone island is formed in titanium alloy substrate and micron diamond is not distributed in the discontinuous distribution of titanium alloy-based bottom surface, nano-diamond layer
The surface and micron diamond island surface on island.Since the hydrogen terminal key that diamond has has certain bactericidal effect, to make
Obtaining diamond coatings also has bactericidal effect, while micron diamond island and nano-diamond layer are formed by multilevel micro-nano knot
Structure has the effect of centainly antibacterial；In addition, also having lower since diamond layer has extremely stable physicochemical properties
Coefficient of friction and higher hardness and elastic modulus so that the titanium that diamond coatings and titanium alloy substrate are compounded to form
Alloy composite materials have excellent biocompatibility, bactericidal effectiveness and corrosion-resistant and abrasion resistance properties.
(2) a kind of surgical implant provided by the utility model, including above-mentioned titanium alloy composite material.It is closed in view of above-mentioned titanium
Advantage possessed by metal/composite material, so that the surgical implant and human body environment have good biocompatibility, antibiotic property
With anticorrosive anti-wear performance, implantation surrounding tissue can't be damaged after being implanted into human body environment and rejection is caused to cause to aggravate disease
Feelings have good medical application prospect.
(3) a kind of medical instrument provided by the utility model, including above-mentioned titanium alloy composite material or surgical implant.Mirror
The advantage possessed by above-mentioned titanium alloy composite material or surgical implant, so that the medical instrument using it is also having the same
Advantage, to have good medical application prospect.
Detailed description of the invention
It, below will be right in order to illustrate more clearly of specific embodiment of the present invention or technical solution in the prior art
Specific embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, it is described below
In attached drawing be that some embodiments of the utility model are not paying creativeness for those of ordinary skill in the art
Under the premise of labour, it is also possible to obtain other drawings based on these drawings.
Fig. 1 is the structural schematic diagram of titanium alloy composite material provided by the utility model；
Fig. 2 is that pseudomonas aeruginosa acts on the SEM electron microscope on titanium alloy composite material provided by the utility model.
Diagram: 100- titanium alloy substrate；200- micron diamond island；300- nano-diamond layer.
Specific embodiment
The embodiments of the present invention are described in detail below in conjunction with embodiment, but those skilled in the art
It will be understood that the following example is merely to illustrate the utility model, and it is not construed as limitation the scope of the utility model.Embodiment
In the person that is not specified actual conditions, carry out according to conventional conditions or manufacturer's recommended conditions.Life is not specified in agents useful for same or instrument
Manufacturer person is produced, is the conventional products that can be obtained by commercially available purchase.
First aspect according to the present utility model provides a kind of titanium alloy composite material, including titanium alloy substrate 100
With the diamond coatings for being formed in titanium alloy-based bottom surface；
Wherein, diamond coatings include being located at the micron diamond island 200 on the same surface of the titanium alloy substrate and receiving
Rice diamond layer 300；
Micron diamond island 200 is discontinuous to be set to 100 surface of titanium alloy substrate；
Nano-diamond layer 300 is set to 200 surface of micron diamond island and titanium alloy substrate 100 is not provided with micron
The surface of Buddha's warrior attendant stone island 200, it is specific as shown in Figure 1.
Titanium alloy specific strength with higher and good biocompatibility, the elasticity modulus of titanium alloy most connects with bone in addition
Closely, therefore it becomes the ideal body implant metal material of comprehensive performance.
Diamond has extremely stable physicochemical properties, lower coefficient of friction, higher hardness and good
Elasticity modulus and bio-compatibility, therefore diamond formation layer structure is modified titanium alloy substrate, it can be with high degree
Improve the corrosion-resistant and abrasion resistance properties of titanium alloy.
Micro-nano structure is primarily referred to as having the function of micron or nanoscale features size, knot of arranging according to ad hoc fashion
Structure.In the present invention, diamond coatings are micron diamond island with micro-meter scale and continuous by Nano diamond
Multiple dimensioned (multilevel, the hierarchical) micro-nano structure that the nano-diamond layer of formation is constituted.Multilevel micro-nano structure can
It is interpreted as by the first order, Nano diamond of micron diamond island being micro-nano structure that the second level is combined.
It should be noted that the micron diamond island in the utility model, can be single partial size and is in micron level
Diamond particles can be the aggregation that multiple partial sizes are in the diamond particles of micron level or Nano grade, be formed by
The partial size of aggregation is still in micron level.
Micron diamond island is discontinuous to be set to titanium alloy-based bottom surface, is primarily referred to as micron diamond island titanium alloy-based
Bottom surface is in the equally distributed state of monodisperse, i.e., there are certain gap and gap sizes between adjacent micron diamond island
Than more consistent, titanium alloy substrate part of the surface is occupied by micron diamond island at this time, titanium alloy-based bottom surface corresponding to gap
It is exposed outside.
Nano-diamond layer is set to micron diamond island surface and titanium alloy substrate is not provided with micron diamond island
Surface, it is continuous on micron diamond island surface and the exposed surface of titanium alloy substrate to be primarily referred to as nano-diamond layer
Distribution.
Micron diamond island and nano-diamond layer, which are formed by multilevel micro-nano structure, has the effect of centainly antibacterial；
And since the hydrogen terminal key of diamond has certain bactericidal effect, so that diamond coatings also have certain bactericidal effect.
In view of advantage possessed by above-mentioned diamond coatings and the characteristic of titanium alloy substrate, so that mainly by above-mentioned Buddha's warrior attendant
The titanium alloy composite material that stone coating and titanium alloy substrate are compounded to form has excellent biocompatibility and bactericidal effectiveness,
From in Fig. 2 it can also be seen that pseudomonas aeruginosa adsorbs death on titanium alloy composite material provided by the utility model, thus
It can prove that titanium alloy composite material has certain anti-microbial property.Meanwhile titanium alloy composite material also has good corrosion resistant
Erosion and abrasion resistance properties.Titanium alloy composite material is applied to bio-medical material and is implanted into human body environment, implantation can't be damaged
Surrounding tissue and cause rejection cause aggravate the state of an illness.
As a kind of optional embodiment of the utility model, the partial size on micron diamond island is 2~5 in diamond coatings
μm, preferably 2.5~4.5 μm, the partial size on typical but non-limiting micron diamond island is 2 μm, 2.5 μm, 3 μm, 4 μm, 4.5
μm or 5 μm.
As a kind of optional embodiment of the utility model, the distance between adjacent micron diamond island less than 2 μm,
Preferably 0.2~1 μm；Between adjacent micron diamond island typical but non-limiting distance be 0.2 μm, 0.4 μm, 0.5 μm,
0.6 μm, 0.8 μm or 1.0 μm.
As a kind of optional embodiment of the utility model, nano diamond coating with a thickness of 50~200nm, preferably
For 100~200nm, the partial size of typical but non-limiting Nano diamond is 50nm, 60nm, 80nm, 100nm, 120nm,
150nm, 180nm or 200nm.
As a kind of optional embodiment of the utility model, the partial size of Nano diamond is 3 in nano diamond coating
~20nm, preferably 6~18nm, the partial size of typical but non-limiting Nano diamond is 3nm, 5nm, 6nm, 8nm, 10nm,
12nm, 15nm, 18nm or 20nm.
By the restriction to micron diamond island partial size, Nano diamond partial size and nano diamond coating thickness, make
Distinctive three-dimensional multistage time micro-nano structure can be formed by obtaining the diamond coatings, be conducive to the modification to titanium alloy-based bottom surface, into
The comprehensive performance of one step promotion titanium alloy composite material.
The material of medical titanium alloy substrate has very much.It is titanium alloy-based as a kind of optional embodiment of the utility model
Bottom is in Ti-6Al-4V titanium alloy substrate, Ti-5Al-2.5Sn titanium alloy substrate or Ti-12Mo-6Zr-2Fe titanium alloy substrate
Any one.
The preparation method of above-mentioned titanium alloy composite material, comprising the following steps:
It will be after pretreated titanium alloy substrate carries out the brilliant processing of primary plant, using chemical vapour deposition technique in titanium alloy
Base part surface forms discrete micron diamond island；
After the product for being formed with discrete micron diamond island is carried out the brilliant processing of secondary plant, using chemical vapor deposition
Method forms nano-diamond layer, obtains titanium alloy composite material.
The concrete type of chemical vapour deposition technique has very much, in the present invention, including but not limited to heated filament or microwave
Plasma enhanced chemical vapor deposition method, preferably hot filament CVD.
Chemical vapour deposition diamond growth needs to be implanted into diamond seeds, and it is raw then to carry out extension in the crystal seed point of implantation
It is long.Wherein epitaxial growth refers to that the diamond in subsequent chemistry vapor deposition processes is grown along the diamond seeds of implantation.
The utility model is prepared by planting crystalline substance twice, being deposited on titanium alloy-based bottom surface twice with multilevel micro-nano knot
The diamond surface of structure, i.e., it is primary to plant brilliant brilliant-secondary chemical vapor deposition of the secondary plant of-chemical vapor deposition-.Wherein, lead to
The primary implant density for planting brilliant control diamond is crossed, to control the life on micron diamond island in a chemical vapor deposition processes
Long distribution, so that discontinuous distribution is presented in titanium alloy-based bottom surface in micron diamond island, that is, micron diamond island is in titanium
Alloy substrates surface uneven distribution；By the secondary implant density for planting brilliant same control diamond, to control secondary chemistry
In vapor deposition processes Nano diamond titanium alloy-based bottom surface and micron diamond island surface growth distribution, thus shape
At continuous nano-diamond layer.
It should be noted that the primary brilliant density of plant for planting crystalline substance is lower than the secondary plant crystalline substance density for planting crystalline substance.
Specifically, before carrying out the brilliant processing of primary plant to titanium alloy substrate, it is also necessary to be carried out to titanium alloy-based bottom surface
Pretreatment.As a kind of optional embodiment of the utility model, pretreatment includes carrying out at sandblasting to titanium alloy-based bottom surface
The step of reason and cleaning；
Blasting treatment is carried out to titanium alloy-based bottom surface, activated matrix surface enables diamond particles to be adsorbed on base
Body surface face, while microcosmic upper increase surface roughness, macroscopically uniform outer surface, can be improved later period diamond coatings with it is titanium alloy-based
Binding force between bottom.The blasting treatment time is preferably 1-5min.
Titanium alloy substrate after blasting treatment is cleaned.Cleaning is first cleaned by ultrasonic 1-3 times with deionized water, each 2-
10min is finally cleaned by ultrasonic 2-10min with alcohol.
Primary crystalline substance of planting is carried out to pretreated titanium alloy substrate to handle.A kind of optional embodiment party as the utility model
Formula, the primary plant crystalline substance density for planting crystalline substance are 106~108A/cm2, preferably (2~8) × 107A/cm2；It is typical but non-limiting
The primary plant crystalline substance density for planting crystalline substance is 1 × 106A/cm2、2×106A/cm2、5×106A/cm2、8×106A/cm2、1×107
A/cm2、2×107A/cm2、5×107A/cm2、8×107A/cm2Or 108A/cm2。
Primary crystalline substance of planting is to make diamond seeds in titanium alloy substrate in monodisperse and equally distributed state, thus one
Discrete micron diamond island is formed after secondary chemical vapor deposition in titanium alloy substrate.
As a kind of optional embodiment of the utility model, the secondary plant crystalline substance density for planting crystalline substance is 108~1014A/cm2,
Preferably 1013~1014A/cm2；The typical but non-limiting primary plant crystalline substance density for planting crystalline substance is 1 × 108A/cm2、5×108
A/cm2、1×109A/cm2、1×1010A/cm2、1×1011A/cm2、1×1012A/cm2、1×1013A/cm2、2×1013
A/cm2、5×1013A/cm2、8×1013A/cm2Or 1014A/cm2。
Secondary plant crystalline substance is to make diamond seeds in titanium alloy-based bottom surface and micron diamond island surface in continuous arrangement
State, to form continuous nano-diamond layer after secondary chemical vapor deposition.
Primary plant is brilliant different with crystalline substance solution is planted used by secondary plant crystalline substance.A kind of optional embodiment party as the utility model
Formula, the primary brilliant solution of the brilliant primary plant used of planting includes following raw material: nano-diamond powder, anionic surfactant and water,
Wherein, nano-diamond powder quality account for it is primary plant the 0.005~0.5% of brilliant solution quality, such as 0.005%, 0.006%,
0.007%, 0.008%, 0.009%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%, anion table
Face activating agent is 10 in the primary concentration planted in brilliant solution-6~10-3Mol/L, such as 10-6mol/L、10-5mol/L、10-4mol/
L or 10-3Mol/L, primary crystalline substance pH value of solution of planting is 2~8；Such as pH2, pH3, pH4, pH5, pH6, pH7 or pH8；
As a kind of optional embodiment of the utility model, anionic surfactant is oxalic acid or citric acid.The yin from
Sub- surfactant by with the primary diamond phase interaction planted in brilliant solution, by diamond titanium alloy-based bottom surface suction
Attached density (planting brilliant density) control is in a certain range.If not adding anionic surfactant or yin in primary plant in brilliant solution
The concentration of ionic surface active agent is lower, then showing for apparent uneven distribution is presented in diamond seeds in titanium alloy substrate
As that is, a large amount of diamond seeds occurs in titanium alloy substrate part of the surface, and part of the surface occurs even without diamond seeds.
It is suitable for planting brilliant solution to plant brilliant monodisperse crystal seed in titanium alloy substrate by selection.Primary plant is brilliant primary by regulation
The zeta current potential for planting brilliant solution keeps the Nano diamond for once planting brilliant solution identical as titanium alloy substrate surface electrical behavior, to adjust
Control discontinuous distribution of the crystal seed in titanium alloy substrate.
It is primary to plant brilliant plant crystal type for pretreated titanium passed through as a kind of optional embodiment of the utility model
Alloy substrates are put into the brilliant solution of primary plant, are dried again after ultrasonic treatment；Preferably, sonication treatment time 20-
60min, drying mode are with being dried with nitrogen；
By planting the brilliant specific restriction for planting crystal type to primary, so that crystal seed can be on titanium alloy substrate surface according to default side
Formula distribution.
After primary plant is brilliant, a chemical vapor deposition is carried out.As a kind of optional embodiment of the utility model, chemistry
It include: gas source includes methane and hydrogen that vapour deposition process, which forms the technological parameter on discrete micron diamond island,；And/or first
Alkane flow is 32-40sccm, and for example, 32sccm, 34sccm, 35sccm, 36sccm, 38sccm or 40sccm, hydrogen flowing quantity is
700-900sccm, for example, 700sccm, 750ccm, 800sccm, 850sccm or 900sccm；And/or silk sample spacing is 6-
12mm, for example, 6mm, 8mm, 10mm, 11mm or 12mm；And/or vacuum chamber pressure 1200-2000Pa, for example,
1200Pa, 1400Pa, 1500Pa, 1600Pa, 1800Pa or 2000Pa；And/or power 6200-6900W, for example,
6200W, 6400W, 6500W, 6600W, 6800W or 6900W；And/or sedimentation time 0.5-1.5h, sedimentation time are, for example,
0.5h, 1.0h or 1.5h.
By controlling a chemical vapor deposition process parameter, so that the low-density monodisperse that titanium alloy-based bottom surface is formed
Plant Jingjing kind on deposit the micron diamond island of high-quality discontinuous distribution.
It is brilliant that the product for being formed with discrete micron diamond island is subjected to secondary plant.It is different from primary crystalline substance solution of planting, two
The secondary secondary plant crystalline substance solution for planting brilliant use includes following raw material: nano-diamond powder, cationic surfactant and water, wherein
Nano-diamond powder quality account for it is secondary plant the 0.005~0.5% of brilliant solution quality, such as 0.005%, 0.006%, 0.007%,
0.008%, 0.009%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%, cationic surfactant
It is 10 in the secondary concentration planted in brilliant solution-6~10-3Mol/L, such as 10-6mol/L、10-5mol/L、10-4Mol/L or 10- 3Mol/L, the brilliant pH value of solution of secondary plant is 3~5；Such as pH3, pH4 or pH5.
As a kind of optional embodiment of the utility model, cationic surfactant is lysine or methacryloxypropyl
Ethyl-trimethyl salmiac, commercially available or voluntarily configuration.The cationic surfactant passes through brilliant molten with secondary plant
Diamond phase interaction in liquid, the adsorption density (planting brilliant density) by diamond seeds in titanium alloy-based bottom surface are controlled one
Determine range.If lower or do not add cationic surfactant in the secondary concentration for planting brilliant anions in solution surfactant,
Then diamond seeds are the phenomenon that can also apparent uneven distribution be presented in titanium alloy substrate and micron diamond island surface.
It is secondary plant it is brilliant by regulating and controlling the secondary zeta current potential for planting brilliant solution, make Nano diamond and titanium alloy-based bottom surface with
And micron diamond island surface electrical behavior on the contrary, be in regulate and control crystal seed in titanium alloy-based bottom surface and micron diamond island surface
Continuously distributed state.
The secondary plant crystal type for planting crystalline substance is brilliant molten for the product for being formed with discrete micron diamond island is put into secondary plant
In liquid, it is dried again after ultrasonic treatment；Preferably, sonication treatment time 20-60min, drying mode are with being dried with nitrogen.
By planting the brilliant specific restriction for planting crystal type to secondary, so that crystal seed can be on exposed titanium alloy substrate surface
And micron diamond island surface is distributed according to predetermined manner.
Secondary chemical vapor deposition is carried out after secondary plant is brilliant.As a kind of optional embodiment of the utility model, chemistry
It includes methane and hydrogen that vapour deposition process, which includes: gas source in the technological parameter of formation nano-diamond layer,；And/or methane 32-
40sccm, for example, 32sccm, 34sccm, 35sccm, 36sccm, 38sccm or 40sccm, hydrogen flowing quantity 700-
900sccm, for example, 700sccm, 750ccm, 800sccm, 850sccm or 900sccm；And/or silk sample spacing is 6-12mm,
For example, 6mm, 8mm, 10mm, 11mm or 12mm；And/or vacuum chamber pressure 1200-2000Pa, for example, 1200Pa,
1400Pa, 1500Pa, 1600Pa, 1800Pa or 2000Pa；And/or power 6200-6900W, for example, 6200W, 6400W,
6500W, 6600W, 6800W or 6900W；And/or sedimentation time 2-10min, for example, 2min, 3min, 4min, 5min,
6min, 8min or 10min.
By controlling secondary chemical vapor deposition process parameter, so that the titanium alloy substrate on not formed micron diamond island
High-quality continuous point is deposited in the plant Jingjing kind that the high density that surface and micron diamond island surface are formed continuously is dispersed
The nano-diamond layer of cloth.
As a preferred embodiment, a kind of preparation method of typical above-mentioned titanium alloy composite material includes following
Step:
(a) titanium alloy-based bottom surface is pre-processed, pretreatment includes carrying out blasting treatment to titanium alloy-based bottom surface
The step of with cleaning；
(b) pretreated titanium alloy substrate is placed in the brilliant solution of primary plant and is carried out after once planting crystalline substance processing, using change
It learns vapour deposition process and forms discrete micron diamond island in titanium alloy substrate part of the surface；
(c) product for being formed with discrete micron diamond island primary plant is placed in carry out in brilliant solution at secondary plant crystalline substance
After reason, Nano diamond is formed in titanium alloy substrate part of the surface and micron diamond island surface using chemical vapour deposition technique
Layer, obtains titanium alloy composite material.
Wherein, the time of blasting treatment is 2-10min in step (a)；
It includes following raw material that brilliant solution is once planted in step (b): nano-diamond powder, anionic surfactant and water,
Wherein, nano-diamond powder quality accounts for the 0.005~0.5% of the brilliant solution quality of primary plant, and anionic surfactant is oxalic acid
Or citric acid, the concentration of anionic surfactant are 10-6~10-3Mol/L, primary to plant brilliant pH value of solution 2-8, planting crystal type is
By pretreated titanium alloy substrate be put into it is primary plant ultrasound 20-60min in brilliant solution, taking-up, with being dried with nitrogen；
The brilliant solution of secondary plant includes following raw material in step (c): nano-diamond powder, cationic surfactant and water,
Wherein, nano-diamond powder quality accounts for the 0.005~0.5% of the brilliant solution quality of secondary plant, and anionic surfactant is to rely ammonia
Acid or MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, the concentration of anionic surfactant are 10-6~10-3Mol/L, it is secondary
Brilliant pH value of solution 3~6 is planted, and planting crystal type is the product for being formed with discrete micron diamond island to be put into the brilliant solution of secondary plant
Ultrasonic 20-60min takes out, with being dried with nitrogen.
The second aspect according to the present utility model, additionally provides a kind of surgical implant, including above-mentioned titanium alloy is compound
Material.
In view of advantage possessed by titanium alloy composite material provided by the utility model, so that the surgical implant and human body
Environment has good biocompatibility, antibiotic property and anticorrosive anti-wear performance, can't damage after being implanted into human body environment
Implantation surrounding tissue and cause rejection cause aggravate the state of an illness, have good medical application prospect, for example, can be applied to orthopaedics,
The subjects such as orthopaedic srugery, cardiovascular and cerebrovascular.
As a kind of optional embodiment of the utility model, surgical implant includes femoral head, hip joint, prosthese, tooth
Orthopedic wire, root canal file, spinal column correction bar, bone plate, intramedullary needle, patella claw, seal wire, guide pin, cardiac patch, intravascular stent, blood
Bolt filter, esophageal stents, respiratory tract bracket, biliary tract rack, urethra rack, rectum bracket, duodenal stent or external auditory canal branch
Any one in frame.
In terms of third according to the present utility model, a kind of medical instrument, including above-mentioned titanium alloy composite wood are additionally provided
Material or above-mentioned surgical implant.
Common medical instrument include but is not limited to scalpel, surgical clamp, operation surgical forceps, thoracic cavity expander, orthopedic instruments,
Pacemaker and defibrillator, nerve stimulator etc..
In view of advantage possessed by above-mentioned titanium alloy composite material or surgical implant, so that using its medical instrument
Advantage having the same, to have good medical application prospect.
Finally, it should be noted that above each embodiment is only to illustrate the technical solution of the utility model, rather than to it
Limitation；Although the utility model is described in detail referring to aforementioned each embodiment, those skilled in the art
It is understood that it can still modify to technical solution documented by aforementioned each embodiment, or to part of or
Person's all technical features are equivalently replaced；And these are modified or replaceed, it does not separate the essence of the corresponding technical solution originally
The range of each embodiment technical solution of utility model.
Claims (10)
1. a kind of titanium alloy composite material characterized by comprising
Titanium alloy substrate and the diamond coatings for being formed in the titanium alloy-based bottom surface；
Wherein, the diamond coatings include the micron diamond island positioned at the same surface of the titanium alloy substrate and nanogold
Hard rock layer；
The micron diamond island is discontinuous to be set to the titanium alloy-based bottom surface；
The nano-diamond layer is set to micron diamond island surface and the titanium alloy substrate be not provided with it is described
The surface on micron diamond island.
2. titanium alloy composite material according to claim 1, which is characterized in that the partial size on the micron diamond island is 2
~5 μm.
3. titanium alloy composite material according to claim 2, which is characterized in that the micron diamond island is single micron
Diamond particles；And/or
The micron diamond island is the aggregation that multiple Nano diamond particles are formed.
4. titanium alloy composite material according to claim 2, which is characterized in that between the adjacent micron diamond island
Distance less than 2 μm.
5. titanium alloy composite material according to claim 1, which is characterized in that the nano diamond coating with a thickness of
50~200nm.
6. titanium alloy composite material described in -5 any one according to claim 1, which is characterized in that the Nano diamond applies
The partial size of Nano diamond is 3~20nm in layer.
7. titanium alloy composite material described in -5 any one according to claim 1, which is characterized in that the titanium alloy substrate is
It is any in Ti-6Al-4V titanium alloy substrate, Ti-5Al-2.5Sn titanium alloy substrate or Ti-12Mo-6Zr-2Fe titanium alloy substrate
It is a kind of.
8. a kind of surgical implant, which is characterized in that including titanium alloy composite material described in claim 1-7 any one.
9. surgical implant according to claim 8, which is characterized in that the surgical implant include wire for correcting shape of tooth,
Root canal file, spinal column correction bar, bone plate, intramedullary needle, patella claw, seal wire, guide pin, cardiac patch, intravascular stent, thrombus filter,
Appointing in esophageal stents, respiratory tract bracket, biliary tract rack, urethra rack, rectum bracket, duodenal stent or external auditory canal bracket
It anticipates one kind.
10. a kind of medical instrument, which is characterized in that including titanium alloy composite material described in claim 1-7 any one or
Surgical implant described in claim 8 or 9.
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Cited By (3)
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| CN110947030A (en) * | 2019-11-29 | 2020-04-03 | 中国科学院深圳先进技术研究院 | Antibacterial multi-grade diamond composite material and preparation method and application thereof |
| CN111334778A (en) * | 2018-12-18 | 2020-06-26 | 深圳先进技术研究院 | Titanium alloy composite material, preparation method thereof, surgical implant and medical instrument |
| WO2021219132A1 (en) * | 2020-04-30 | 2021-11-04 | Master Dynamic Limited | Anti contaminant coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111334778A (en) * | 2018-12-18 | 2020-06-26 | 深圳先进技术研究院 | Titanium alloy composite material, preparation method thereof, surgical implant and medical instrument |
| CN111334778B (en) * | 2018-12-18 | 2024-02-09 | 深圳先进技术研究院 | Titanium alloy composite material, preparation method thereof, surgical implant and medical instrument |
| CN110947030A (en) * | 2019-11-29 | 2020-04-03 | 中国科学院深圳先进技术研究院 | Antibacterial multi-grade diamond composite material and preparation method and application thereof |
| CN110947030B (en) * | 2019-11-29 | 2021-11-16 | 中国科学院深圳先进技术研究院 | Antibacterial multi-grade diamond composite material and preparation method and application thereof |
| WO2021219132A1 (en) * | 2020-04-30 | 2021-11-04 | Master Dynamic Limited | Anti contaminant coating |
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