CN108277518A - A kind of micro-arc oxidation electrolyte and reduce the brittle method of micropore ceramics film layer - Google Patents
A kind of micro-arc oxidation electrolyte and reduce the brittle method of micropore ceramics film layer Download PDFInfo
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- CN108277518A CN108277518A CN201810235991.XA CN201810235991A CN108277518A CN 108277518 A CN108277518 A CN 108277518A CN 201810235991 A CN201810235991 A CN 201810235991A CN 108277518 A CN108277518 A CN 108277518A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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Abstract
The invention discloses a kind of micro-arc oxidation electrolyte, including sodium glycero-phosphate, calcium acetate, chitin nano whisker, de- N acetyl chitosan and disodium ethylene diamine tetraacetate, a concentration of the 0.05~1.0% of chitin nano whisker.A concentration of the 0.05~0.5% of de- N acetyl chitosans.Invention additionally discloses a kind of brittle methods of reduction micropore ceramics film layer, including（1）Pretreated light metal or its alloy material are placed in above-mentioned micro-arc oxidation electrolyte, low temperature differential arc oxidation processing is carried out；Fully washing, is downloaded into sodium hyaluronate solution in negative pressure by it after drying, keeps negative pressure state 18~30 hours, washs and is drying to obtain after taking-up.The present invention by being added chitin nano whisker and/or de- N acetyl chitosan in the electrolytic solution, it is set to be evenly distributed in ceramic film in low temperature bidirectional pulse micro-arc oxidation process, again high molecular polymer not soluble in water is generated with Sodium Hyaluronate crosslinking under vacuum, the toughness for improving ceramic film prevents bending embrittlement and fragmentation.
Description
Technical field
The present invention relates to micropore ceramics film layer preparing technical fields, more particularly to a kind of micro-arc oxidation electrolyte and reduction
The brittle method of micropore ceramics film layer.
Background technology
Differential arc oxidation or plasma electrolytic oxidation surface ceramic deposition technology, since its is easy to operate, condition is controllable and ring
Border is friendly, has started to be applied to, using the metals such as titanium, magnesium, aluminium and its alloy as the surgery medical implant surface of material, to prepare
Ceramic film with micropore, this pore structure can also promote sticking, be proliferated and breaking up for cell quite convenient for carrying medicine.But
As the ceramic film of the micropore prepared with calcination method, there is also same for the micropore ceramics film layer which prepares
Defect, i.e. brittleness, easy to crack frangible, toughness is poor.No matter which kind of proximate matter pure titanium and its alloy are（As silk material, tubing, column material,
Web, bulk, plank etc.）Micropore ceramics film layer implant, when outer force effect causes its bending, the ceramic film in knee
Different degrees of embrittlement can occur and split broken.This is because the composition of ceramic film is made of ionic bond and covalent bond crystal grain
Polycrystalline material, anti-crack, the ability very little of Resisting fractre.In addition, the pore structure of height is also easy to cause ceramic film brittleness
Increase.If the fragmentation product of ceramic film is into blood, it is possible to lead to the blocking of capillary.
Method in relation to medical implant micropore ceramics film layer toughening mainly has three categories method both at home and abroad at present：1, add
Enter method, i.e., toughening material such as long fibre, staple fiber, inorganic crystal whisker or inorganic nanoparticles etc. is added in ceramic slurry, so
High-temperature roasting, calcining are carried out afterwards, improve the brittleness of ceramic film with this, but be difficult and the physics of matrix, change since material is added
Compatibility matching is learned, and the problem of the kind of material be added, toxicity, biocompatibility and biological degradability etc., is made
It is above restricted in the application of medicine；2, infusion process is coated, i.e., the coating dipping macromolecular on micropore ceramics reticular structure（It is high
Molecularly Imprinted Polymer, gelatin, chitosan, silk-like proteins etc.）Organic coating can increase the tough of micropore ceramics film layer to a certain extent
Property, but either organic macromolecule or large biological molecule, it is required to the toxicants such as formaldehyde, glutaraldehyde and makees crosslinking agent, this
It is set above to be extremely limited in the application of medicine.3, basic zirconium chloride is added in differential arc oxidation liquid, it can be in film layer using it
It is middle to generate the zirconium dioxide with certain toughening effect, the mechanical property of ceramic film is improved, but this method is only in micropore ceramics
Some improvement are done in terms of the compression strength of film layer, toughening effect is still limited, especially when external force causes micropore ceramics film layer
When bending, or unavoidably split broken phenomenon.
It can be seen that in terms of the above-mentioned existing brittle improvement of micropore ceramics layer, there are still inconvenient and defects, and urgently add
To be further improved.How to found a kind of new micro-arc oxidation electrolyte and reduces the brittle method of micropore ceramics film layer, at
Improved target is needed for current industry pole.
Invention content
The technical problem to be solved in the present invention is to provide a kind of micro-arc oxidation electrolyte, make it to reduce micropore ceramics film layer
Brittleness play an important role, to overcome the shortcomings of existing micro-arc oxidation electrolyte.
In order to solve the above technical problems, the present invention provides a kind of micro-arc oxidation electrolyte, including sodium glycero-phosphate and acetic acid
Calcium, the molar ratio of sodium glycero-phosphate and calcium acetate is 1 in the electrolyte：2~1：22.
As an improvement of the present invention, further include chitin nano whisker, the chitin nano whisker accounts for the electricity
The mass percent concentration for solving liquid is 0.05~1.0%.
It is further improved, further includes de- N- acetyl chitosans, the de- N- acetyl chitosan accounts for the quality of the electrolyte
Percent concentration is 0.05~0.5%, and the viscosity average molecular weigh of the de- N- acetyl chitosan is 10K.
It is further improved, further includes disodium ethylene diamine tetraacetate, the disodium ethylene diamine tetraacetate accounts for the electrolyte
Mass percent concentration is 0.1~3.0%.
It is further improved, electrolyte ammonium hydroxide tune pH to 10~12.
The technical issues of present invention also solves be to provide it is a kind of it is easy to operate, safely and effectively to reduce micropore ceramics film layer crisp
Property method, so that its micropore ceramics film layer toughness obtained is improved, be not susceptible to embrittlement and split it is broken, to overcome existing micropore
The deficiency of ceramic film preparation method.
In order to solve the above technical problems, the present invention provides a kind of brittle method of reduction micropore ceramics film layer, the method
Include the following steps：
（1）Pretreated light metal or its alloy material are placed in as in above-mentioned micro-arc oxidation electrolyte, it is micro- to carry out low temperature
Arc oxidation processes；
（2）After differential arc oxidation, by the light metal with micropore ceramics film layer being prepared or its alloy material spend from
Sub- water vibrates washing repeatedly, and removes moisture removal, drying for standby；
（3）The dry light metal with micropore ceramics film layer or its alloy material are placed in vacuum tank, height is downloaded into negative pressure
Molecular weight hyaluronic acid sodium solution, and keep negative pressure state 18~30 hours, the light metal or its alloy material are taken out, is spent
Ionized water vibrates washing repeatedly, and removes moisture removal, dry to get light metal or its alloy material with required micropore ceramics film layer
Material.
It is further improved, the step（1）The pre-treatment step of middle light metal or its alloy material is：By light metal or its
Alloy material is placed in 5mol/L sodium hydroxide solutions, and 12~36 hours are kept the temperature in 80~100 DEG C of water baths, to remove light gold
Belong to the attachment and oil stain on material.It then takes out, is rinsed repeatedly with deionized water, until pH value is neutrality, then at ultrasonic wave
Middle deionized water supersound washing repeatedly, until supersound washing water is limpid.
It is further improved, the step（1）Middle low temperature differential arc oxidation processing step uses bidirectional pulse differential arc oxidation system
It carries out,
In the bidirectional pulse differential arc oxidation system, the voltage magnitude of direct impulse is 0~+800 volts, the voltage of reverse impulse
Amplitude is 0~-800 volts, and pulse frequency is 100~1000 hertz, and power supply duty ratio is 10~90%.
It is further improved, the step（1）The temperature of electrolyte described in middle low temperature differential arc oxidation processing step is not higher than 8
℃。
It is further improved, the step（3）Described in sodium hyaluronate solution mass percent concentration be 0.01~
1.0%。
It is further improved, the light metal is titanium, magnesium or aluminium, and the light metal or its alloy material are silk material, tubing, column
Material, web, bulk or plate construction.
It is further improved, the method further includes step（4）：Take the step（3）Obtained light metal or its alloy material
Material, to the chitin nano whisker in its ceramic film internal structure and in film surface and micropore hole wall, carry out whiosker pullout,
Crack deflection or the processing of crackle bridging.
The present invention inventive concept and inventive principle be：
It is the product that natural polymer chitin takes off N- acetyl that N- acetyl chitosans are taken off in the present invention, has good bio-compatible
Property, biological degradability and antibacterial, hemostasis and promote the excellent properties such as wound healing, be applied to biological medicine, food is defended
The fields such as life, household chemicals, however its biomechanical property is poor, its application is made to be restricted.
Chitin nano whisker is to pass through chemistry the methods of such as acidolysis, enzymolysis and physics system by polysaccharide chitin in the present invention
Standby obtained rodlike or acicular nanoscale whisker, average length 280nm, average diameter 17nm, draw ratio is 16 or so.
Chitin nano whisker other than keeping the good biocompatibility of chitin, biological degradability and the characteristics such as positively charged,
Mechanical strength is equal to the intensity that adjacent interatomic force generates, and therefore, also has high intensity, high-modulus, high-flexibility and high drawing
Rate and good dispersibility.
Chitin nano whisker belongs to organic crystalline palpus, and organic crystalline must be with inorganic crystal whisker in polymer-function material, resistance
It is used widely in thermal resistance combustible material and papermaking material, but rarely seen organic crystalline must be used for ceramic composite and metal-based compound
The activeness and quietness of material.This is because traditional ceramics are compound and MANUFACTURING METHODS OF METAL-MATRIX COMPOSITES is long-time high-temperature roasting
And calcining, organic crystalline must be easily degraded, be ashed.And the method that the differential arc oxidation that the present invention uses prepares cermet film layer, it is
By the combination of electrolyte and corresponding electrical parameter, the part that metal surface is generated by arc light power generation, moment, high temperature,
High pressure acts on, and grows the ceramic film with micropore based on substrate metal oxide.
Specifically, micro-arc oxidation process is classified approximately into three phases.（1）Anodic oxidation：Under electric field action, material surface
It is preliminary to generate layer oxide film, and bulk gas and bubble are generated, at this time in addition to equably oozing in titanium oxide film layer structure
Thoroughly, the cationic such as calcium, phosphorus and sodium be distributed, inlayed in electrolyte are outer, also equally equably permeate, are distributed, inlay band
The chitin nano whisker and macromolecular of positive charge take off N- acetyl chitosans；（2）Spark discharge：Material surface generates a large amount of unstable
Surely the white arc light to drift about, when voltage reaches critical point, nascent oxide ceramic film layer is broken down by high-voltage, high temperature and pressure microdot
（Spot）Oxidation film is caused to melt, cooling electrolyte moment takes away heat, and fusant quick solidification is formed micro- in material surface
Hole ceramic film.With thickening for film layer, chitin nano whisker and macromolecular take off N- acetyl chitosan and calcium, phosphorus and sodium
Distribution in film layer is also stepped up；（3）Micro-arc discharge：Arc light reddens at this time, aoxidizes further to percdation, micropore is opened
Beginning is mutually communicated, and forms fine conductive path.These fine accesses are conducive to the infiltration and immersion of hyaluronic acid after differential arc oxidation.
It can be seen that by the above process, under conditions of electrolyte is in low temperature, the high temperature that differential arc oxidation generates has microdot（Spot）Property, wink
Intersexuality, fugitive property, this characteristic make organic crystalline must i.e. chitin nano whisker（Also include that macromolecular takes off N- acetyl chitosans）, no
It can degrade and be ashed easily, be titanium oxide ceramic film toughening, prevent bending is broken from providing architecture basics.
In turn, hyaluronic acid is a kind of negatively charged straight chain polymer being widely distributed in tissue in the present invention
Polysaccharide, aqueous solution have the rheological properties such as high resiliency, high viscosity, are widely used to field of medicaments.The present invention is in vacuum
Under the conditions of, negatively charged hyaluronic acid and positively charged de- N- acetyl chitosan and/or chitin nano whisker can make pottery
Network shaped polymer is generated in porcelain film layer, is played together with chitin nano whisker and is reduced micropore ceramics film layer brittleness phenomenon, together
When also have good biocompatibility and biological degradability, promote sticking, be proliferated and breaking up for cell.
By adopting such a design, the present invention has at least the following advantages：
The present invention makes crust by the way that chitin nano whisker and/or de- N- acetyl chitosan are added in micro-arc oxidation electrolyte
Plain nano whisker and/or de- N- acetyl chitosan are in low temperature bidirectional pulse micro-arc oxidation process, with complicated electrochemistry, thermalization
It learns, plasma chemical reaction, is evenly distributed on using light metal or its alloy as the metal oxide ceramic film layer structure of matrix
In, while being also embedded on film surface and film layer micropore hole wall；It is generated not with Sodium Hyaluronate crosslinking under vacuum again
It is dissolved in the high molecular polymer of water, which is firmly embedded in ceramic film internal structure and film layer and hole wall surface
On, various light metal shape materials can be improved（Including silk material, tubing, column material, web, bulk, plank etc.）Surface ceramic film layer band
The toughness for having the surgery medical implant of micropore prevents bending embrittlement and fragmentation.Simultaneously because the de- N- acetyl that surface is dispersed with
The polymer of chitosan and Sodium Hyaluronate has good biocompatibility and biological degradability, convenient for carrying medicine, is also conducive to cell
Stick, be proliferated and break up, solve existing medical implant micropore ceramics film layer brittleness problems and biocompatibility and life
Object degradability there are the problem of.
The present invention reduces the brittle method of micropore ceramics film layer, easy to operate, safe and effective.
Description of the drawings
The above is merely an overview of the technical solutions of the present invention, in order to better understand the technical means of the present invention, below
In conjunction with attached drawing, the present invention is described in further detail with specific implementation mode.
Fig. 1 is the Electronic Speculum image scanning figure for the pure titanium surgery medical implant with micropore ceramics film layer that comparative example obtains.
Fig. 2 is that the Electronic Speculum imaging of the pure titanium surgery medical implant of micropore ceramics film layer needed for band that embodiment 1 obtains is swept
Tracing.
Fig. 3 is that the pure titanium surgery medical implant with micropore ceramics film layer that comparative example obtains is carried in hardness test HV1kg
Impression figure under lotus.
Fig. 4 is the pure titanium surgery medical implant of micropore ceramics film layer needed for band that embodiment 1 obtains in hardness test
Impression figure under HV10kg load.
Specific implementation mode
Embodiment 1
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
Pure titanium medical implant silk material in 5mol/L sodium hydroxide solutions, it is small to be kept the temperature 24 by step 1 in 80 DEG C of water baths
When, it is then rinsed repeatedly with deionized water, until pH is neutral.In ultrasonic wave, with deionized water supersound washing repeatedly, until
Supersound washing water is limpid.
Step 2 carries out differential arc oxidation using bidirectional pulse micro-arc oxidation device to pure titanium medical implant silk material surface.
The bidirectional pulse micro-arc oxidation device is made of pulse mao power source cabinet, electrolytic cell, cooling system and stirring system.With electricity
Stainless steel polar plate in slot is solved pure titanium material is clamped as anode using special special fixture, the bidirectional pulse differential of the arc is arranged as cathode
It is 1000 hertz to aoxidize power pulse frequency, and the duty ratio corresponding period is 50%, powers on, opens the system of being quickly cooled down,
Under conditions of micro-arc oxidation electrolyte temperature is kept not higher than 8 DEG C, bidirectional pulse is carried out to pure titanium medical implant silk material surface
Differential arc oxidation.When positive voltage reaches 390 volts, negative voltage reaches 21 volts, power supply is closed.
Wherein, every liter of micro-arc oxidation electrolyte contains 4.32 grams of sodium glycero-phosphate, 35.23 grams of calcium acetate, chitin nanometer
5.0 grams of whisker, de- 5.0 grams of N- acetyl chitosan, 3.72 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Step 3 vibrates the pure titanium surgery medical implant Jing Guo Microarc Oxidation Surface Treatment with deionized water repeatedly
Washing removes remaining electrolyte in film surface and micropore, then uses negative pressure method, pumps moisture, drying for standby.
Dry ceramic film surface is carried the pure titanium surgery medical implant of micropore, is placed in vacuum tank by step 4,
It is downloaded into 0.1% in negative pressure（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 24 hours, make high molecular weight
Sodium Hyaluronate and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, carry out abundant
Cross-linking reaction.It then takes out, vibrates washing repeatedly with deionized water, remove remaining unbonded in film surface and micropore
Then Sodium Hyaluronate uses negative pressure method, pump moisture, dry to get the pure medical plant of titanium surgery with required micropore ceramics film layer
Enter body.
Embodiment 2
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
Step 1 in 5mol/L sodium hydroxide solutions, keeps the temperature titanium alloy medical implant tubing in 100 DEG C of water baths
It 12 hours, is then rinsed repeatedly with deionized water, until pH is neutral.With deionized water supersound washing repeatedly in ultrasonic wave,
Until supersound washing water is limpid.
Step 2 carries out differential of the arc oxygen using bidirectional pulse micro-arc oxidation device to titanium alloy medical implant tube surfaces
Change.With embodiment 1, the power pulse frequency that the bidirectional pulse micro-arc oxidation device is arranged is the bidirectional pulse micro-arc oxidation device
500 hertz, the duty ratio corresponding period is 10%.Power on, open the system of being quickly cooled down, in micro-arc oxidation electrolyte temperature
Under conditions of keeping not higher than 8 DEG C, bidirectional pulse differential arc oxidation is carried out to titanium alloy surgery medical implant surface.Work as positive voltage
Reach 380 volts, negative voltage is when reaching 21 volts, close power supply.
Wherein, every liter of micro-arc oxidation electrolyte contains 8.64 grams of sodium glycero-phosphate, 35.33 grams of calcium acetate, chitin nanometer
1.0 grams of whisker, de- 5.0 grams of N- acetyl chitosan, 3.02 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Step 3 shakes the titanium alloy medical implant tubing Jing Guo Microarc Oxidation Surface Treatment with deionized water repeatedly
Washing is swung, remaining electrolyte in film surface and micropore is removed, negative pressure method is then used, pumps moisture, drying for standby.
Dry ceramic film surface is carried the titanium alloy medical implant tubing of micropore, is placed in vacuum tank by step 4
In, it is downloaded into 0.5% in negative pressure（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 18 hours, make high score
Son amount Sodium Hyaluronate and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, carry out
Sufficient cross-linking reaction.It then takes out, vibrates washing repeatedly with deionized water, remove and remaining in film surface and micropore do not tie
Then the Sodium Hyaluronate of conjunction uses negative pressure method, pump moisture, and drying is medical to get the titanium alloy with required micropore ceramics film layer
Implant.
Embodiment 3
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
The medical embedded scapus material of pure titanium in 5mol/L sodium hydroxide solutions, it is small to be kept the temperature 36 by step 1 in 80 DEG C of water baths
When, it is then rinsed repeatedly with deionized water, until pH is neutral.Then in ultrasonic wave with deionized water supersound washing repeatedly, directly
It is limpid to supersound washing water.
Step 2 carries out differential arc oxidation using bidirectional pulse micro-arc oxidation device to pure titanium medical embedded scapus material surface.
For the bidirectional pulse micro-arc oxidation device with embodiment 1, the power pulse frequency that the bidirectional pulse micro-arc oxidation device is arranged is 200
Hertz, the duty ratio corresponding period is 90%.Power on, open the system of being quickly cooled down, is kept in micro-arc oxidation electrolyte temperature
Under conditions of 8 DEG C, bidirectional pulse differential arc oxidation is carried out to pure titanium surgery medical embedded scapus material surface.When positive voltage reaches
When reaching 21 volts to 380 volts, negative voltage, power supply is closed.
Wherein, every liter of micro-arc oxidation electrolyte contains 2.08 grams of sodium glycero-phosphate, 35.20 grams of calcium acetate, chitin nanometer
0.5 gram of whisker, de- 5.0 grams of N- acetyl chitosan, 1.02 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Step 3, by the medical embedded scapus material of pure titanium surgery Jing Guo Microarc Oxidation Surface Treatment, repeatedly with deionized water
Oscillation washing, removes remaining electrolyte in film surface and micropore, then uses negative pressure method, pumps moisture, dry.
Dry ceramic film surface is carried the surgery medical implant of micropore, is placed in vacuum tank by step 4, in negative
Pressure is loaded into 0.01%（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 30 hours, keep high molecular weight saturating
Bright matter acid sodium and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, carry out sufficient
Cross-linking reaction.It then takes out, vibrates washing repeatedly with deionized water, remove remaining unbonded saturating in film surface and micropore
Then bright matter acid sodium uses negative pressure method, pump moisture, dry to get the pure titanium medical implant with required micropore ceramics film layer.
Embodiment 4
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
Step 1 in 5mol/L sodium hydroxide solutions, keeps the temperature titanium alloy medical implant web in 100 DEG C of water baths
It 24 hours, is then rinsed repeatedly with deionized water, until pH is neutral.Then in ultrasonic wave, with deionized water, ultrasound is washed repeatedly
It washs, until supersound washing water is limpid.
Step 2 carries out differential of the arc oxygen using bidirectional pulse micro-arc oxidation device to titanium alloy medical implant web surface
Change.With embodiment 1, the power pulse frequency that the bidirectional pulse micro-arc oxidation device is arranged is the bidirectional pulse micro-arc oxidation device
100 hertz, duty ratio corresponding period 50%.Power on, open the system of being quickly cooled down, is protected in micro-arc oxidation electrolyte temperature
Under conditions of holding not higher than 8 DEG C, bidirectional pulse differential arc oxidation is carried out to titanium alloy surgery medical implant surface.When positive voltage reaches
When reaching 21 volts to 390 volts, negative voltage, power supply is closed.
Wherein, every liter of micro-arc oxidation electrolyte contains 4.36 grams of sodium glycero-phosphate, 35.30 grams of calcium acetate, chitin nanometer
10.0 grams of whisker, de- 0.5 gram of N- acetyl chitosan, 3.50 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Step 3 shakes the titanium alloy medical implant web Jing Guo Microarc Oxidation Surface Treatment with deionized water repeatedly
Washing is swung, remaining electrolyte in film surface and micropore is removed, negative pressure method is then used, pumps moisture, it is dry.
Dry ceramic film surface is carried the titanium alloy medical implant web of micropore, is placed in vacuum tank by step 4
In, it is downloaded into 1.0% in negative pressure（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 24 hours, make high score
Son amount Sodium Hyaluronate and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, carry out
Sufficient cross-linking reaction.It then takes out, vibrates washing repeatedly with deionized water, remove and remaining in film surface and micropore do not tie
Then the Sodium Hyaluronate of conjunction uses negative pressure method, pump moisture, dry to get the titanium alloy surgery with required micropore ceramics film layer
Medical implant.
Embodiment 5
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
Pure titanium medical implant bulk in 5mol/L sodium hydroxide solutions, it is small to be kept the temperature 24 by step 1 in 80 DEG C of water baths
When, it is then rinsed repeatedly with deionized water, until pH is neutral.Then in ultrasonic wave, with deionized water supersound washing repeatedly, directly
It is limpid to supersound washing water.
Step 2 carries out differential of the arc oxygen using bidirectional pulse micro-arc oxidation device system to pure titanium medical implant bulk surface
Change.With embodiment 1, the power pulse frequency that the bidirectional pulse micro-arc oxidation device is arranged is the bidirectional pulse micro-arc oxidation device
50 hertz, duty ratio corresponding period 90%.Power on, open the system of being quickly cooled down, is kept in micro-arc oxidation electrolyte temperature
Under conditions of 8 DEG C, bidirectional pulse differential arc oxidation is carried out to pure titanium surgery medical implant surface.When positive voltage reaches
380 volts, negative voltage is when reaching 21 volts, close power supply.
Wherein, every liter of micro-arc oxidation electrolyte contains 8.60 grams of sodium glycero-phosphate, 35.42 grams of calcium acetate, chitin nanometer
5.0 grams of whisker, de- 5.0 grams of N- acetyl chitosan, 30.66 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Surgery medical implant Jing Guo Microarc Oxidation Surface Treatment is vibrated washing with deionized water by step 3 repeatedly,
Remaining electrolyte in film surface and micropore is removed, negative pressure method is then used, pumps moisture, it is dry.
Dry ceramic film surface is carried the surgery medical implant of micropore, is placed in vacuum tank by step 4, in negative
Pressure is loaded into 0.1%（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 24 hours, keep high molecular weight transparent
Matter acid sodium and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, are adequately handed over
Connection reaction.It then takes out, vibrates washing repeatedly with deionized water, remove remaining unbonded transparent in film surface and micropore
Then matter acid sodium uses negative pressure method, pump moisture, dry to get the pure titanium surgery medical implant with required micropore ceramics film layer.
Embodiment 6
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
Pure titanium medical implant plank in 5mol/L sodium hydroxide solutions, it is small to be kept the temperature 24 by step 1 in 80 DEG C of water baths
When, it is then rinsed repeatedly with deionized water, until pH is neutral.Then in ultrasonic wave with deionized water supersound washing repeatedly, directly
It is limpid to supersound washing water.
Step 2 carries out differential of the arc oxygen using bidirectional pulse micro-arc oxidation device system to pure titanium medical implant material surface
Change.With embodiment 1, the power pulse frequency that the bidirectional pulse micro-arc oxidation device is arranged is the bidirectional pulse micro-arc oxidation device
1000 hertz, duty ratio corresponding period 75%.Power on, open the system of being quickly cooled down, is protected in micro-arc oxidation electrolyte temperature
Under conditions of holding not higher than 8 DEG C, bidirectional pulse differential arc oxidation is carried out to pure titanium surgery medical implant surface.When positive voltage reaches
380 volts, negative voltage is when reaching 21 volts, close power supply.
Wherein, every liter of micro-arc oxidation electrolyte contains 18.28 grams of sodium glycero-phosphate, 35.38 grams of calcium acetate, chitin nanometer
5.0 grams of whisker, de- 5.0 grams of N- acetyl chitosan, 30.70 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Surgery medical implant Jing Guo Microarc Oxidation Surface Treatment is vibrated washing with deionized water by step 3 repeatedly,
Remaining electrolyte in film surface and micropore is removed, negative pressure method is then used, pumps moisture, it is dry.
Dry ceramic film surface is carried the surgery medical implant of micropore, is placed in vacuum tank by step 4, in negative
Pressure is loaded into 0.1%（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 24 hours, keep high molecular weight transparent
Matter acid sodium and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, are adequately handed over
Connection reaction.It then takes out, vibrates washing repeatedly with deionized water, remove remaining unbonded transparent in film surface and micropore
Then matter acid sodium uses negative pressure method, pump moisture, dry to get the pure titanium surgery medical implant with required micropore ceramics film layer.
Embodiment 7
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
Titanium alloy medical implant silk material in 5mol/L sodium hydroxide solutions, 24 is kept the temperature in 80 DEG C of water baths by step 1
Hour, it is then rinsed repeatedly with deionized water, until pH is neutral.Then in ultrasonic wave with deionized water supersound washing repeatedly,
Until supersound washing water is limpid.
Step 2 carries out the differential of the arc using bidirectional pulse micro-arc oxidation device system to titanium alloy medical implant material surface
Oxidation.The power pulse frequency of the bidirectional pulse micro-arc oxidation device is arranged with embodiment 1 in the bidirectional pulse micro-arc oxidation device
It is 1000 hertz, duty ratio corresponding period 25%.Power on, open the system of being quickly cooled down, in micro-arc oxidation electrolyte temperature
Under conditions of keeping not higher than 8 DEG C, bidirectional pulse differential arc oxidation is carried out to titanium alloy surgery medical implant surface.Work as positive voltage
Reach 380 volts, negative voltage is when reaching 21 volts, close power supply.
Wherein, every liter of micro-arc oxidation electrolyte contains 14.38 grams of sodium glycero-phosphate, 35.20 grams of calcium acetate, chitin nanometer
5.0 grams of whisker, de- 2.5 grams of N- acetyl chitosan, 3.68 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Surgery medical implant Jing Guo Microarc Oxidation Surface Treatment is vibrated washing with deionized water by step 3 repeatedly,
Remaining electrolyte in film surface and micropore is removed, negative pressure method is then used, pumps moisture, it is dry.
Dry ceramic film surface is carried the surgery medical implant of micropore, is placed in vacuum tank by step 4, in negative
Pressure is loaded into 0.1%（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 24 hours, keep high molecular weight transparent
Matter acid sodium and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, are adequately handed over
Connection reaction.It then takes out, vibrates washing repeatedly with deionized water, remove remaining unbonded transparent in film surface and micropore
Then matter acid sodium uses negative pressure method, pump moisture, and drying is medical embedded to get the titanium alloy surgery with required micropore ceramics film layer
Body.
Embodiment 8
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
Step 1 in 5mol/L sodium hydroxide solutions, protects titanium alloy medical implant wire materials in 80 DEG C of water baths
Temperature 24 hours, is then rinsed with deionized water repeatedly, until pH is neutral.Then with deionized water, ultrasound is washed repeatedly in ultrasonic wave
It washs, until supersound washing water is limpid.
Step 2 carries out the differential of the arc using bidirectional pulse micro-arc oxidation device system to titanium alloy medical implant material surface
Oxidation.The power pulse frequency of the bidirectional pulse micro-arc oxidation device is arranged with embodiment 1 in the bidirectional pulse micro-arc oxidation device
It is 1000 hertz, duty ratio corresponding period 25%.Power on, open the system of being quickly cooled down, in micro-arc oxidation electrolyte temperature
Under conditions of keeping not higher than 8 DEG C, bidirectional pulse differential arc oxidation is carried out to titanium alloy surgery medical implant surface.Work as positive voltage
Reach 380 volts, negative voltage is when reaching 21 volts, close power supply.
Wherein, every liter of micro-arc oxidation electrolyte contains 21.60 grams of sodium glycero-phosphate, 35.23 grams of calcium acetate, chitin nanometer
5.0 grams of whisker, de- 5.0 grams of N- acetyl chitosan, 3.72 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Surgery medical implant Jing Guo Microarc Oxidation Surface Treatment is vibrated washing with deionized water by step 3 repeatedly,
Remaining electrolyte in film surface and micropore is removed, negative pressure method is then used, pumps moisture, it is dry.
Dry ceramic film surface is carried the surgery medical implant of micropore, is placed in vacuum tank by step 4, in negative
Pressure is loaded into 0.1%（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 24 hours, keep high molecular weight transparent
Matter acid sodium and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, are adequately handed over
Connection reaction.It then takes out, vibrates washing repeatedly with deionized water, remove remaining unbonded transparent in film surface and micropore
Then matter acid sodium uses negative pressure method, pump moisture, and drying is medical embedded to get the titanium alloy surgery with required micropore ceramics film layer
Body.
Embodiment 9
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
Pure titanium medical implant silk material in 5mol/L sodium hydroxide solutions, it is small to be kept the temperature 24 by step 1 in 80 DEG C of water baths
When, it is then rinsed repeatedly with deionized water, until pH is neutral.Then in ultrasonic wave with deionized water supersound washing repeatedly, directly
It is limpid to supersound washing water.
Step 2 carries out differential of the arc oxygen using bidirectional pulse micro-arc oxidation device system to pure titanium medical implant material surface
Change.With embodiment 1, the power pulse frequency that the bidirectional pulse micro-arc oxidation device is arranged is the bidirectional pulse micro-arc oxidation device
1000 hertz, duty ratio corresponding period 25%.Power on, open the system of being quickly cooled down, is protected in micro-arc oxidation electrolyte temperature
Under conditions of holding not higher than 8 DEG C, bidirectional pulse differential arc oxidation is carried out to pure titanium surgery medical implant surface.When positive voltage reaches
380 volts, negative voltage is when reaching 21 volts, close power supply.
Wherein, every liter of micro-arc oxidation electrolyte contains 20.59 grams of sodium glycero-phosphate, 35.24 grams of calcium acetate, chitin nanometer
5.0 grams of whisker, de- 5.0 grams of N- acetyl chitosan, 3.60 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Surgery medical implant Jing Guo Microarc Oxidation Surface Treatment is vibrated washing with deionized water by step 3 repeatedly,
Remaining electrolyte in film surface and micropore is removed, negative pressure method is then used, pumps moisture, it is dry.
Dry ceramic film surface is carried the surgery medical implant of micropore, is placed in vacuum tank by step 4, in negative
Pressure is loaded into 0.1%（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 24 hours, keep high molecular weight transparent
Matter acid sodium and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, are adequately handed over
Connection reaction.It then takes out, vibrates washing repeatedly with deionized water, remove remaining unbonded transparent in film surface and micropore
Then matter acid sodium uses negative pressure method, pump moisture, dry to get the pure titanium surgery medical implant with required micropore ceramics film layer.
Embodiment 10
A kind of brittle new method of reduction micropore ceramics layer, includes the following steps：
Pure titanium medical implant silk material in 5mol/L sodium hydroxide solutions, it is small to be kept the temperature 24 by step 1 in 80 DEG C of water baths
When, it is then rinsed repeatedly with deionized water, until pH is neutral.Then in ultrasonic wave with deionized water supersound washing repeatedly, directly
It is limpid to supersound washing water.
Step 2 carries out differential of the arc oxygen using bidirectional pulse micro-arc oxidation device system to pure titanium medical implant material surface
Change.With embodiment 1, the power pulse frequency that the bidirectional pulse micro-arc oxidation device is arranged is the bidirectional pulse micro-arc oxidation device
1000 hertz, duty ratio corresponding period 25%.Power on, open the system of being quickly cooled down, is protected in micro-arc oxidation electrolyte temperature
Under conditions of holding not higher than 8 DEG C, bidirectional pulse differential arc oxidation is carried out to pure titanium surgery medical implant surface.When positive voltage reaches
380 volts, negative voltage is when reaching 21 volts, close power supply.
Wherein, every liter of micro-arc oxidation electrolyte contains 22.60 grams of sodium glycero-phosphate, 35.23 grams of calcium acetate, chitin nanometer
1.0 grams of whisker, de- 5.0 grams of N- acetyl chitosan, 3.82 grams of disodium ethylene diamine tetraacetate, with ammonium hydroxide tune pH to 10~12.
Surgery medical implant Jing Guo Microarc Oxidation Surface Treatment is vibrated washing with deionized water by step 3 repeatedly,
Remaining electrolyte in film surface and micropore is removed, negative pressure method is then used, pumps moisture, it is dry.
Dry ceramic film surface is carried the surgery medical implant of micropore, is placed in vacuum tank by step 4, in negative
Pressure is loaded into 0.1%（w/w）High molecular weight sodium hyaluronate solution, and keep negative pressure state 24 hours, keep high molecular weight transparent
Matter acid sodium and film layer inside and the de- N- acetyl chitosan and chitin nano whisker of film layer and hole wall surface, are adequately handed over
Connection reaction.It then takes out, vibrates washing repeatedly with deionized water, remove remaining unbonded transparent in film surface and micropore
Then matter acid sodium uses negative pressure method, pump moisture, dry to get the pure titanium surgery medical implant with required micropore ceramics film layer.
Comparative example
The comparative example and above-described embodiment 1 the difference is that, be added not in micro-arc oxidation electrolyte and take off N- acetyl chitosans
With chitin nano whisker, other steps are identical, obtain the pure titanium surgery medical implant with micropore ceramics film layer.
As a result example 1
The band that the pure titanium surgery medical implant and comparative example of micropore ceramics film layer needed for the band obtained to above-described embodiment 1 obtain
The pure titanium surgery medical implant of micropore ceramics film layer, carry out Electronic Speculum image scanning, electron-microscope scanning figure as shown in figure 1 and 2, from
Attached Fig. 1 and 2 can be seen that the micropore ceramics surface for the pure titanium surgery medical implant with micropore ceramics film layer that comparative example obtains can
See slight crack, the micropore ceramics surface of the pure titanium surgery medical implant of micropore ceramics film layer needed for the band that embodiment 1 obtains has no
Slight crack can then show that the micropore ceramics film layer obtained by using micro-arc oxidation electrolyte of the present invention is not likely to produce embrittlement.
As a result example 2
The pure titanium surgery medical implant of micropore ceramics film layer and comparative example needed for the band that above-described embodiment 1,3,7 obtains is chosen to obtain
The pure titanium surgery medical implant with micropore ceramics film layer arrived arbitrarily selects to carry out Vickers hardness at 5 per a sample（Brittleness）
Detection detects Vickers under the different loads of Stupalox using 401MVD digital displays micro Vickers, HVS-50 Vickers
Hardness, detection foundation is 16534 standards of GB/T, while observing vickers indentation feature.The result is shown in the following table 1 and attached drawing 3,4.
1 micropore ceramics film layer Vickers hardness of table（Brittleness）Test result
It can be seen that from result, the hardness and toughness of the micropore ceramics film layer obtained using micro-arc oxidation electrolyte of the present invention are had very
It is big to improve, a degree of plastic deformation can be generated, stress concentration is passivated, which is avoided that because under certain outer force effect
Embrittlement and fragmentation.
The present invention utilizes low temperature bidirectional pulse differential arc oxidization technique, makes chitin nano whisker and the macromolecular in electrolyte
De- N- acetyl chitosans are evenly distributed on complicated electrochemistry, heat chemistry, plasma chemical reaction with pure titanium or titanium conjunction
In the golden titanium oxide ceramic film structure for matrix, while being also embedded on film surface and film layer micropore hole wall, it is then sharp
It can be crosslinked with negatively charged hyaluronic acid with the chitin nano whisker of positive charge and de- N- acetyl chitosan is carried
Reaction generates the polymeric structure of cubic network shape, in titanium oxide ceramics film layer internal structure and film surface and micropore hole
Dimensional network structure is formed between ceramic crystalline grain in wall, the active force and caching power to make molecule interchain are strengthened；When by
When causing pure titanium or titanium alloy substrate to be bent to external force, which occurs a degree of plastic deformation, absorbs very big portion
The exceptionally energy of force effect is passivated stress concentration, makes toughened unit（Ceramic film）It avoids destroying because deforming more than its limit.
In addition, the invention also includes to being widely distributed in titanium oxide ceramics film layer internal structure and film surface and micropore
Chitin nano whisker in hole wall the effects that by whiosker pullout, crack deflection and crackle bridging, makes the toughness of ceramic film
Further enhanced.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, this
Field technology personnel make a little simple modification, equivalent variations or modification using the technology contents of the disclosure above, all fall within this hair
In bright protection domain.
Claims (12)
1. a kind of micro-arc oxidation electrolyte, which is characterized in that including sodium glycero-phosphate and calcium acetate, glycerine phosphorus in the electrolyte
The molar ratio of sour sodium and calcium acetate is 1：2~1：22.
2. a kind of micro-arc oxidation electrolyte according to claim 1, which is characterized in that further include chitin nano whisker,
The mass percent concentration that the chitin nano whisker accounts for the electrolyte is 0.05~1.0%.
3. a kind of micro-arc oxidation electrolyte according to claim 1 or 2, which is characterized in that further include that de- N- acetyl shells are poly-
Sugar, the mass percent concentration that the de- N- acetyl chitosan accounts for the electrolyte is 0.05~0.5%, and the de- N- acetyl
The viscosity average molecular weigh of chitosan is 10K.
4. a kind of micro-arc oxidation electrolyte according to claim 3, which is characterized in that further include ethylenediamine tetra-acetic acid two
Sodium, the mass percent concentration that the disodium ethylene diamine tetraacetate accounts for the electrolyte are 0.1~3.0%.
5. a kind of micro-arc oxidation electrolyte according to claim 4, which is characterized in that the electrolyte with ammonium hydroxide tune pH extremely
10~12.
6. a kind of brittle method of reduction micropore ceramics film layer, which is characterized in that described method includes following steps：
（1）Pretreated light metal or its alloy material are placed in such as claim 2 to 5 any one of them differential arc oxidation electricity
It solves in liquid, carries out low temperature differential arc oxidation processing；
（2）After differential arc oxidation, by the light metal with micropore ceramics film layer being prepared or its alloy material spend from
Sub- water vibrates washing repeatedly, and removes moisture removal, drying for standby；
（3）The dry light metal with micropore ceramics film layer or its alloy material are placed in vacuum tank, height is downloaded into negative pressure
Molecular weight hyaluronic acid sodium solution, and keep negative pressure state 18~30 hours, the light metal or its alloy material are taken out, is spent
Ionized water vibrates washing repeatedly, and removes moisture removal, dry to get light metal or its alloy material with required micropore ceramics film layer
Material.
7. a kind of brittle method of reduction micropore ceramics film layer according to claim 6, which is characterized in that the step
（1）The pre-treatment step of middle light metal or its alloy material is：Light metal or its alloy material are placed in 5mol/L sodium hydroxides
In solution, 12~36 hours are kept the temperature in 80~100 DEG C of water baths, takes out, is then rinsed repeatedly with deionized water, until pH value
For neutrality, with deionized water supersound washing repeatedly in ultrasonic wave, until supersound washing water is limpid.
8. a kind of brittle method of reduction micropore ceramics film layer according to claim 6, which is characterized in that the step
（1）Middle low temperature differential arc oxidation processing step is carried out using bidirectional pulse differential arc oxidation system,
In the bidirectional pulse differential arc oxidation system, the voltage magnitude of direct impulse is 0~+800 volts, the voltage of reverse impulse
Amplitude is 0~-800 volts, and pulse frequency is 100~1000 hertz, and power supply duty ratio is 10~90%.
9. a kind of brittle method of reduction micropore ceramics film layer according to claim 8, which is characterized in that the step
（1）The temperature of electrolyte described in middle low temperature differential arc oxidation processing step is not higher than 8 DEG C.
10. a kind of brittle method of reduction micropore ceramics film layer according to claim 6, which is characterized in that the step
（3）Described in sodium hyaluronate solution mass percent concentration be 0.01~1.0%.
11. a kind of brittle method of reduction micropore ceramics film layer according to claim 6, which is characterized in that the light gold
It is titanium, magnesium or aluminium to belong to, and the light metal or its alloy material are silk material, tubing, column material, web, bulk or plate construction.
12. a kind of brittle method of reduction micropore ceramics film layer according to claim 6, which is characterized in that the method
It further include step（4）：Take the step（3）Obtained light metal or its alloy material, in its ceramic film internal structure and
Chitin nano whisker in film surface and micropore hole wall carries out whiosker pullout, crack deflection or the processing of crackle bridging.
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| CN111020672A (en) * | 2019-11-30 | 2020-04-17 | 长沙新材料产业研究院有限公司 | Micro-arc oxidation process for Mg-Gd-Y magnesium alloy |
| CN111690972A (en) * | 2019-03-06 | 2020-09-22 | 苏州鱼得水电气科技有限公司 | Processing technology of high-temperature-resistant ceramic oxide film |
| CN112089888A (en) * | 2020-09-17 | 2020-12-18 | 杭州协合医疗用品有限公司 | Chitin whisker reinforced hyaluronic acid cytoskeleton and preparation method thereof |
| KR20210098295A (en) * | 2020-01-31 | 2021-08-10 | 창원대학교 산학협력단 | Chitosan used in electrolytic plasma process of magnesium alloy |
| CN115055697A (en) * | 2022-06-08 | 2022-09-16 | 佳木斯大学 | Preparation method of super-hydrophilic micro-nano surface of nickel-titanium implant for 3D printing |
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| CN112089888A (en) * | 2020-09-17 | 2020-12-18 | 杭州协合医疗用品有限公司 | Chitin whisker reinforced hyaluronic acid cytoskeleton and preparation method thereof |
| CN115055697A (en) * | 2022-06-08 | 2022-09-16 | 佳木斯大学 | Preparation method of super-hydrophilic micro-nano surface of nickel-titanium implant for 3D printing |
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