CN109481105A - A kind of sealer and manufacturing method and angiocarpy bracket with compression - Google Patents
A kind of sealer and manufacturing method and angiocarpy bracket with compression Download PDFInfo
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- CN109481105A CN109481105A CN201811292326.0A CN201811292326A CN109481105A CN 109481105 A CN109481105 A CN 109481105A CN 201811292326 A CN201811292326 A CN 201811292326A CN 109481105 A CN109481105 A CN 109481105A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
- A61F2/90—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
- A61F2/91—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00011—Metals or alloys
- A61F2310/00035—Other metals or alloys
- A61F2310/00041—Magnesium or Mg-based alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00389—The prosthesis being coated or covered with a particular material
- A61F2310/00395—Coating or prosthesis-covering structure made of metals or of alloys
- A61F2310/00419—Other metals
- A61F2310/00473—Coating made of zinc or Zn-based alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00389—The prosthesis being coated or covered with a particular material
- A61F2310/00592—Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
- A61F2310/00796—Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Cardiology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Vascular Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Optics & Photonics (AREA)
- Physics & Mathematics (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a kind of sealer with compression and manufacturing method and angiocarpy bracket, the surface of the basis material of angiocarpy bracket is arranged in sealer, and corrosion rate is lower than the corrosion rate of basis material, and sealer has the prestressing force of pressure.Manufacturing method: introducing compression or sealer introduce compression after being coated during the sealer is coated and generates.The damage of stress corrosion and corrosion fatigue of magnesium or magnesium alloy angiocarpy bracket sealer can effectively be inhibited by implementing the present invention, reduced the stress corrosion rate of sealer, can especially be inhibited the phenomenon that spot corrosion, and comprehensive, uniform corrosion is maintained.
Description
Technical field
The invention belongs to the technical field of medical instrument, in particular to a kind of sealer with compression and
Manufacturing method and angiocarpy bracket.
Background technique
According to WHO(2017 cardiovascular disease) described in: caused by cardiovascular disease is heart and vascular disorder, including coronary heart disease
(heart attack), cerebrovascular disease (apoplexy), hypertension, peripheral vascular disease, rheumatic heart disease, congenital heart disease, the heart
Force failure and cardiomyopathy.According to WHO report, since 2012, the annual whole world has 1,7,700,000 people to die of cardiovascular patient, accounts for
The 31% of general mortality rate, 80% or more the cardiovascular disease death rate is derived from heart disease and cerebral apoplexy, annual 70 years old global or less dead
37% is derived from cardiovascular disease in non-communicable diseases.Cardiovascular disease is the public great hygienic issues in China.China is cardiovascular
Number of patients is more than 2.3 hundred million (2/10 adults), annual 3000000 or more cardiovascular death.
The pathogenesis of coronary heart disease is primarily due to coronary artery stenosis, and deficiency myocardial blood supply is caused to cause angina pectoris, the rhythm of the heart
Not normal, myocardial infarction or even crisis life.Treatment method mainly has drug, minimally invasive intervention (balloon dilatation, Stent)
And Coronary Artery Bypass.Since cardiovascular morbidity is high, cardiovascular intervention apparatus product technology exploitation and industry development are very
Rapidly.2008 so far, and coronary artery bracket product has been sure to occupy global single medical device product sales volume first.Future market is huge
Greatly.
Percutaneous coronary endoluminal vascular urethroptasty succeeds for the first time within 1977.The bare metal stent eighties in last century is born, as
Permanent support is implanted into human vas, including coronary artery, support blood vessels prevent restenosis.Certainly also there is rejection, implantation office
Portion's chronic inflammation, vessel endothelialisation slow down, and gradually appear restenosis (nearly 30%).Permanent metal timbering material by stainless steel by
Gradually develop to cochrome, Nitinol, ferroalloy, magnesium alloy etc..
The beginning of this century, bracket for eluting medicament are born.By anti-cell proliferation agents rapamycin or derivative, taxol coating
(coating) is in bracket (high molecular polymer carrier-polystyrene-isobutene, polyethylene-vinyl acetate PEVAC, poly- methyl-prop
Enoic acid ter-butyl ester PBMA, phosphocholine (PAC) reduce restenosis rate by the sustained release of drug to a certain extent, it is suppressed that
Smooth muscle cell hyper-proliferative reduces the formation of early stage thrombus.
Due to the side effect of bare metal stent, gaining rate, long-term anticoagulant needs again, after bracket for eluting medicament drug release is complete
Bare metal stent side effect reproduces, and the research of biodegradable angiocarpy bracket rises at the sound.Biodegradable angiocarpy bracket
It after referring to stenter to implant human body, interacts with blood, the body fluid of human body, under various biological zymetology effects, when by one section
Between after, be corroded or degrade, that is to say, that be gradually dissolved in blood and body fluid, be absorbed by the body or arranged through body discharges system
Out, bracket finally disappears in the blood vessel.Degradable angiocarpy bracket has been inherently eliminated stenter to implant blood due to degradable
The problem of Guan Hou, reangiostenosis, and bracket can be implanted into repeatedly, degrades, be implanted into again, then degrade.
Biodegradable angiocarpy can be divided into two kinds by substrate, and high molecular material biodegradable stent and metal material can drop
Solve bracket.The material of high molecular material biodegradable stent mainly has, PLLA, PLGA, PC, PCL, PHBV, PAGA, POE etc..It is high
After molecular material biodegradable stent is implanted into human body, can be degraded, catabolite enters tricarboxylic acid cycle, generate CO2 and
H2O.Clinically more mature is polylactic acid (such as PLLA), polyglycolic acid (PLGA), ratifies to list by U.S. FDA.
Its main problem is that intensity is low, and thickness is high, thus vascular permeability sectional area reduce and ray to be not through rate low to be unfavorable for PCI
Operation.
The main material of metal biodegradable stent is the alloy of magnesium, iron, zinc, at present based on magnesium alloy.Magnesium and magnesium alloy
Advantage be: 1, magnesium is compared with iron, zinc, or degradation rate is most fast；2, magnesium is one of necessary element of Human Physiology, the second weight
Cation is wanted, internal safe dose is big (intake of 320-420 mg/day)；3, anti-arrhythmia, antithrombus formation；4, magnesium alloy
Mechanical strength is good, and specific strength and specific stiffness are higher, elasticity modulus 41-45GPa and yield strength 65-100MPa, with mankind's bone class
Seemingly.
Magnesium with the shortcomings that magnesium alloy also exactly its to corrode or degrade rate too fast so that blood vessel collapses or breaks before plastotype
It splits.The magnesium alloy angiocarpy bracket of size suitable with stainless steel stent then completely lost its mechanical strength at one month or so, and
It is 6 months or so that ideal angiocarpy bracket, which is kept for the time of its mechanical strength,.Currently, reduction magnesium and magnesium alloy are intracorporal in people
Corroding or degrading rate is an important, active research topic.The study found that impurity element, Fe, Ni, Cu, Co,
Etc. one of an important factor for being influence magnesium and corrosion resistance of magnesium alloy.The highest content for controlling these harmful elements can greatly drop
The rate of low magnesium and magnesium alloy corroded or degraded.
The method for corroding or degrading rate of another kind control magnesium and magnesium alloy is that surface is modified.The modified basic think of in surface
Want to increase one or more layers coating in magnesium or Mg alloy surface；The speed ratio magnesium corroded or degraded of surface covering in human body
Or magnesium alloy is slowly more.Surface covering protects the main structure of magnesium or magnesium alloy bracket not by the blood or corrosion in body fluid of human body
Or degradation, it is maintained its mechanical strength.Ideally surface covering was corroded or degraded at 6 months or so and finishes, naked
Reveal the matrix of magnesium or magnesium alloy；Thereafter the matrix of magnesium or magnesium alloy is in one to two month by the blood or degraded by body fluid of human body.Reason
The rate curve that corrodes or degrades thought is shown in Fig. 1.
There are many modified methods in surface reported in the literature, and important is apply on the surface of magnesium or magnesium alloy metallic support
The corrosion rate in blood of human body and body fluid of protective layer, protective layer is significantly less than magnesium and magnesium alloy.Protective layer material has: gold
Belong to (such as zinc or kirsite)；Ceramic (such as magnesia)；With organic polymer (such as poly-lactic acid ester etc.).Many experimental datas
Show that sealer substantially reduces the angiocarpy bracket of magnesium or magnesium alloy in the corrosion rate imitated in human fluid.
But when people are according to magnesium or magnesium alloy angiocarpy bracket made of imitation human fluid's corrosion experiment design data
When doing animal Implantation Test, they often have found the corrosion rate in animal blood vessels of angiocarpy bracket than they predict
It is high.One of its reason may be corrosion corrosion not instead of not in general sense of the angiocarpy bracket in arteries, stress
Corrosion, even fatigue stress are corroded, it may also be said to be corrosion fatigues.
For angiocarpy bracket during being implanted into human body artery blood vessel, the bracket of reticular structure is in contraction state before this.
It is transported to the stenosis of blood vessel when contraction state along blood vessel for the ease of it.It has arrived at hemadostewnosis, intravascular stent is by it
In ball Nang strut.During distracted, intravascular stent experienced very big deformation.Deformation produces the matrix of magnesium or magnesium alloy
Raw flexible deformation, flexible deformation refers to recoverable deformation, and the flexible deformation of metal generally can only achieve 0.2%；0.2% it
Outside, metal must be completed by being plastically deformed, and plastic deformation is expendable deformation or permanent deformation.Metal is at it
Very big plastic deformation can be born before fracture, specifically for magnesium or magnesium alloy, generally in 5%-10% or so.And magnesium or magnesium close
The coating protective layer of gold surface then may not be able to bear together big deformation with magnesium or magnesium alloy substrate, especially apply to surface
The ceramic material of protective layer.Intravascular stent surface coating protective layer is likely to generate micro-crack during it is softened.Branch
Another mechanism that micro-crack above frame surface coating protective layer generates is that rack surface coating protective layer is coated at it
During the defect that generates.
After in stenter to implant human body artery blood vessel, by heart blood impulse action, alternating expansion and contraction.In breathing space
Between, the micro-crack on the protective layer of rack surface coating is opened, and blood and body fluid enter the tip of fine fisssure, in answering for crack tip
Corrosion reaction occurs for magnesium or magnesium alloy below power concentrated area and coating protective layer even protective layer.In reduced domain, bracket
The micro-crack closure of the protective layer on surface, blood and body fluid are extruded micro-crack with the product of corrosion reaction.Next time
Section is expanded, micro-crack is again turned on, and the corrosion and passivation layer at micro-crack tip is torn, and exposes the fresh object not being passivated
Matter；Blood and body fluid fresh simultaneously flows to crack tip and corrosion reaction occurs for the fresh substance not being passivated.Again
Reduced domain, blood and body fluid are extruded micro-crack with corrosion reaction product again.So alternate expansion and contraction are accelerated
The extension of micro-crack, ultimately causes the breakage of sealer.It can be seen that the expansion and contraction of blood vessel greatly accelerate
The corrosion of sealer；Moreover, the expansion and contraction of blood vessel are even more the corruption promoted around crizzle or defect
Erosion, rather than comprehensive, uniform corrosion.Once sealer is pierced in micro-crack or fault location, magnesium or magnesium below
Alloy is exposed, and the corrosion rate specific surface protective layer of magnesium and magnesium alloy is many fastly, and magnesium or magnesium alloy are corroded soon, table
Face protective layer just loses effect substantially.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides one kind to be able to suppress magnesium or magnesium alloy angiocarpy bracket surface protection
The sealer of the damage of stress corrosion and the corrosion fatigue of layer.
To achieve the above object, the present invention uses following scheme:
A kind of sealer with compression, is used for angiocarpy bracket, and the sealer is arranged in angiocarpy bracket
Basis material surface, corrosion rate is lower than the corrosion rate of basis material, and the sealer has pre- answering for pressure
Power.
Further, the material of the sealer is metal, metal oxide, inorganic compound or organic polymer
One of or it is several.
Further, the performance coating is one or more layers.
The present invention also provides a kind of manufacturing method of sealer with compression, sealer is arranged in painstaking effort
The surface of the basis material of pipe holder, which is characterized in that the sealer introduces pressure during being coated and generating and answers
Power.
Further, in the technical process for applying and generating protective layer, basis material is made to be in the shape being mechanically stretched
After the technical process of state, coating and generation protective layer, the mechanical tensile forces of basis material are discharged, so that generating pressure in protective layer
Stress.
Further, the protective layer is zinc layers or zinc alloy layer, and described matrix material is magnesium or magnesium alloy；Coating and life
At the technique of protective layer are as follows: the surface of magnesium or the angiocarpy bracket of magnesium alloy materials by plating mode carry out coating zinc layers or
Galvanized alloy layer.
Further, the protective layer is magnesium oxide layer, and described matrix material is magnesium or magnesium alloy；Coating and generation protection
The technique of layer are as follows: using the surface for the angiocarpy bracket for impregnating magnesium or magnesium alloy materials in hydrofluoric acid to generate magnesium oxide layer.
Further, the basis material of metal material is heated to high temperature first, applies and generate at high temperature and protects ceramics
Sheath；Then environment temperature is cooled the temperature to, since the thermal expansion coefficient of metal is greater than the thermal expansion coefficient of ceramics, ceramics protection
Compression is generated in layer.
Further, firstly, at ambient temperature, applying biological glass on the surface of basis material using sol-gal process
Glass；It is then heated to high temperature, sintering a few hours generate the bio-vitric layer in fine and close and few cavity；It is cooled to environment temperature, due to
The thermal expansion coefficient of basis material is greater than bio-vitric thermal expansion coefficient, generates extrusion stress in bio-vitric layer.
Further, firstly, applying hydroxyapatite on the surface of basis material using slurry coating method；It is then heated to
500-600 °C, sintering a few hours generate the hydroxyapatite layer in fine and close and few cavity；It is cooled to environment temperature, due to basis material
Thermal expansion coefficient be greater than hydroxyapatite, extrusion stress is generated in hydroxyapatite layer.
Further, on the surface of basis material, the 0.01-5 micron using ion injection method injection other materials is small
Particle generates and squeezes prestressing force.
Further, when using magnesium or when being used as basis material of magnesium alloy, the little particle of the other materials of injection is potassium
One of particle, calcium particle or sodium particle are several.
The invention further relates to the manufacturing method of another sealer with compression, the sealer is applied
Compression is introduced after applying.
Further, firstly, by the basis material of surface coating organic polymer；Then it is slowly drawn at a temperature of medium temperature
It stretches, basis material generates flexible deformation, and organic polymer generates Creep Plastic deformation；When being stretched to deformation length < 0.2%, drop
Then temperature discharges rapidly pulling force to environment temperature or low temperature, basis material and organic polymer generate elastical retraction simultaneously, due to
The Creep Plastic deformation that organic polymer generates during medium temperature slow stretching, organic polymer coating are rapidly elastic in low temperature
After reply, inside generates extrusion stress.
The invention further relates to a kind of angiocarpy bracket, surface is arranged just like surface protection described in claim 1-14
Layer.
The utility model has the advantages that
Prestressing force, negative prestressing force, or perhaps the prestressing force being pressurized is added in sealer, inhibits magnesium or magnesium alloy angiocarpy
The damage of stress corrosion and the corrosion fatigue of rack surface protective layer.In this way when angiocarpy bracket expands in angiocarpy
It waits, reduce a possibility that generating crizzle or the probability of micro-crack occurs；Even if in the case where there is micro-crack, in blood vessel
When expansion, under the action of compression of the micro-crack of superficial layer in superficial layer, do not open, or reduce the journey opened
Degree.The prestressing force being pressurized in sealer, reduces the stress corrosion rate of sealer, can especially inhibit spot corrosion
Phenomenon maintains comprehensive, uniform corrosion.
Detailed description of the invention
Fig. 1 is the degradation rate curve of ideal degradable angiocarpy bracket of the invention；
Fig. 2 is that stress under the influence of cardiac pulses, in rack surface protective layer changes with time；
Fig. 3 is the organic polymer of magnesium or magnesium alloy substrate and the coating of its surface, during medium temperature, slow stretching and low
Temperature discharges rapidly stress-strain diagram during pulling force.
Specific embodiment
To keep purpose and the technical solution of the embodiment of the present invention clearer, below in conjunction with the attached of the embodiment of the present invention
Figure, is clearly and completely described the technical solution of the embodiment of the present invention.Obviously, described embodiment is of the invention
A part of the embodiment, instead of all the embodiments.Based on described the embodiment of the present invention, those of ordinary skill in the art
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of being not necessarily to creative work.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, all terms used herein (including technology art
Language and scientific term) there is meaning identical with the general understanding of those of ordinary skill in fields of the present invention.Should also
Understand, those terms such as defined in the general dictionary, which should be understood that, to be had and the meaning in the context of the prior art
The consistent meaning of justice, and unless defined as here, it will not be explained in an idealized or overly formal meaning.
After Fig. 2 shows that the prestressing force being pressurized is added in intravascular stent sealer, sealer is in cardiac pulses blood flow
Under the influence of, the case where internal stress.In the prestressed situation of no pressure, sealer under the influence of cardiac pulses,
Tensile stress and compression are alternately present at any time, and crizzle opening and closing is alternately present.In the case where there is the prestressed situation of pressure,
Sealer is in compressive stress state under the influence of cardiac pulses always, and the micro-crack in superficial layer is closed always.
Two classes can be divided by introducing the prestressed method being pressurized in magnesium or magnesium alloy angiocarpy bracket sealer:
(1) compression is introduced in the technical process that sealer is coated.(2) pressure is introduced after sealer has been coated
Stress.
(1) method that compression is introduced in the technical process that sealer is coated is divided into 3 kinds again:
(1.1) mechanical stretching method: angiocarpy bracket generally has reticular structure.Manufacturing reticular structure can be there are two types of method.One
It is that reticular structure is made by metal wire.Second is that carving out reticular structure with laser or chemical attack on metal tube.Surface protection
Layer can the wire surface coated in magnesium or magnesium alloy.The material of surface coating layer can be metal, such as zinc；It can be pottery
Porcelain, such as magnesium fluoride；It is also possible to organic polymer, such as poly-lactic acid ester.The coating method of sealer is varied, can
To be plating, such as electrogalvanizing；It can be chemical plating, such as chemical plating magnesium fluoride；It can be spray coating method, sol-gal process, very
Empty coating method etc..
Our mechanical stretching method is to make magnesium or magnesium alloy metal wire in tensional state using mechanical device, in tensional state
Lower coated surfaces protective layer.The material of protective layer can be metallic zinc listed by upper section, and magnesium fluoride ceramics or organic polymer are poly-
Lactate.Coated technique can be plating listed by upper section, chemical plating, spraying, collosol and gel and vacuum coating.The width of stretching
Degree is limited to the elastic deformation area of metal, that is to say, that the deformation less than 0.2%.After coating process, cancel tensional state,
Magnesium or magnesium alloy substrate elastical retraction, so that matrix surface overlay is by compression.
Electrogalvanizing: corrosion rate of the zinc in human vas is lower than magnesium and magnesium alloy, and zinc is also rich content in human body
Element.It is zinc-plated on the surface of magnesium or magnesium alloy, it is to reduce one of magnesium or the effective ways of Corrosion Behaviors of Magnesium Alloys degradation rate.But such as
Fruit zinc protective layer has breakage, exposed magnesium or magnesium alloy substrate and surface zinc protective layer to form electrochemical cell.Magnesium atom loses
Electronics becomes magnesium ion and dissolves in blood, and the electronics lost is then flowed out from zinc protective layer, becomes hydrogen in conjunction with the hydrogen ion in blood.
It can be seen that surface zinc protective layer is once damaged, just loses it and protect magnesium or the uncorroded function of magnesium alloy substrate.Surface
Compression is introduced in zinc layers, can inhibit the opening of micro-crack in the zinc layers of surface, and blood and body fluid are impermeable to crack tip, resistance
The generation of stress corrosion is stopped.
Electrogalvanizing is a mature technique, there is the supplier of many equipment and electroplate liquid.The difference of our techniques
It is, the wire rod of the magnesium or magnesium alloy that are plated is in tensional state.Mechanical device for stretching wire rod can be various.
The strain of stretching should < 0.2%.
Magnesium fluoride.Magnesium fluoride coating is the effectively method for slowing down magnesium or Corrosion Behaviors of Magnesium Alloys rate.Plate magnesium fluoride
Simple process: the wire rod of magnesium or magnesium alloy is placed in a few hours in hydrofluoric acid.Our method the difference is that, magnesium or
The wire rod of magnesium alloy is in tensional state.Mechanical device for stretching wire rod can be various.The strain of stretching should <
0.2%。
(1.2) heating: magnesium or magnesium alloy first can be processed into bare bracket, coated with ceramic layer, coated at high temperature
Environment temperature is cooled to after journey.Since the thermal expansion coefficient of magnesium or magnesium alloy is higher than ceramic material, magnesium or magnesium alloy substrate
Shrinkage ratio surface ceramic caused by as cooling is big, and surface ceramic overlay holds extruded stress.
Such as it is bio-vitric (Bioglass) or hydroxyapatite (hydroxylapatite) is naked coated in magnesium or magnesium alloy
The surface of bracket, bio-vitric can pass through slurry semar technique by sol-gal process, hydroxyapatite.After coating,
It is sintered under high temperature, such as 500-600 °C of a few hours.Sintering is cooled to environment temperature after forming fine and close few empty ceramic layer.Magnesium
Thermal expansion coefficient be 26-28 10-6/ °C, and ceramics thermal expansion coefficient generally between 6-8 10-6/ °C.Assuming that from
525 °C are cooled to 25 °C, and temperature difference is 500 °C, and the difference of thermal expansion coefficient is 20 10-6/ °C, therefore is answered caused by cooling down
Become 20 e-6 x 500=0.01=1%, has been more than the amplitude of magnesium alloy flexible deformation 0.2%.
For example magnesia (MgO) first is generated in the rack surface of magnesium or magnesium alloy.The generation method of magnesia can be sun
Pole oxidation, differential arc oxidation.Then the magnesium of magnesium oxide coating or the bracket of magnesium alloy are being exposed to 200 °C of vapor on surface
Middle a few hours.Vapor and magnesia effect, are changed into magnesium hydroxide (Mg (OH) 2) for magnesia.After reaction, it is cooled to
Environment temperature.The estimation of similar upper section, straining caused by cooling is 0.35%, has also exceeded the width of magnesium alloy flexible deformation 0.2%
Degree.
(1.3) surface particle injection method: fine particle, size are squeezed into the bracket of magnesium or magnesium alloy at 0.01 to 1 micron
Surface.Squeezing into for fine particle causes the surface of magnesium or magnesium alloy in compression.Fine particle can be any material, because micro-
Small particles are to cause mechanical extrusion stress.But fine particle is preferably the element for being easier to corrode than magnesium, small in this way
Particle is corroded prior to magnesium, to protect the matrix of magnesium or magnesium alloy.
Data are normal electrode voltage (Standard Electrode Potential) in table above, opposite hydrogen
Gas.Numerical value is more negative, easier in dielectric solution to lose electronics and become cation.Have 7 in element more more negative than magnesium
It is a.Wherein potassium, calcium, sodium are elements abundant in human body.The method of surface particle injection can use ion implantation.
(2) method of compression is introduced after sealer has been coated:
(2.1) pulling method: after sealer is coated, matrix and surface coating layer are integrally formed.But the mechanics of two layers of substance
Property is different, specifically they stress-strain diagram it is different, especially when rate of deformation is slower, ess-strain is bent
Line is different.
Fig. 3 is the stress-strain diagram of two kinds of substances.Two kinds of substances first is that metal such as magnesium or magnesium alloy, are brackets
Body portion material.Two kinds of substances second is that organic polymer, is the surface coating layer material of bracket.Metal and organic polymer
All flexible deformation, i.e., restorative deformation, after stress is cancelled, strain is returned to zero point.Metal and organic polymer have plasticity
Deformation, i.e. irrecoverability deform, and strain cannot be returned to zero point after stress is cancelled, and leave permanent deformation.The surrender of metal
Stress, i.e. material bear elastically-deformable maximum stress compared with organic polymer height.But metal and organic polymer are answered in its stress
The property of the creep for being most a difference in that them on varied curve is different.
Creep refers to material when lower than its yield stress, and the low speeds flow of material is plastic deformation.Creep temperature compared with
Gao Shi, when will be generally above 50% absolute melting point of material, especially close to its fusing point when, or in very slow strain rate
When can achieve very big degree.The creep of metal, because its fusing point is high, in general environment temperature or a little higher than environment temperature,
Such as 100 degrees Celsius, creep is very little, it is difficult to be measured.And organic polymer is then different.It is taken the photograph 100
Family name's degree or so, material become very soft, flow under very low stress, and stiff when this deformation, expendable.
Using the difference of the creeping property of metal and organic polymer, we can be in 100 degrees centigrades, with slower
Strain rate stretches the linear material of magnesium or magnesium alloy coated with organic polymer, or has been processed into the bracket of type.
This at a slow speed, in the drawing process of medium temperature, magnesium or magnesium alloy substrates are flexible deformations, almost without the plastic deformation of creep；And
Most of deformation of organic polymer may be the plastic deformation of creeping property.At the end of prolonged slow stretching, terminate
It puts us to select lower than 0.2%, i.e. temperature is first dropped to environment temperature, even lower than environment temperature by the yield strain of metal material
Degree, such as zero degree degree Celsius, then discharge pulling force.The process of pulling force release is rapid.In the process of rapid pulling force release
In, magnesium or magnesium alloy occur elasticity and restore, numerical value of the size restoration to before stretching.But the organic polymer size on surface is then
The numerical value that cannot be restored to before stretching.In environment temperature or zero degree, during the release of rapid pulling force, the organic polymer on surface
Elastic recovery can only occur for object；Because previous deformation at a slow speed, in the drawing process of medium temperature is plastic deformation, rapidly,
After flexible deformation during the stretching release of low temperature, the organic polymer on surface is squeezed, and generates compression.
The above is only embodiments of the present invention, and the description thereof is more specific and detailed, and but it cannot be understood as right
The limitation of the invention patent range.It should be pointed out that for those of ordinary skill in the art, not departing from the present invention
Under the premise of design, various modifications and improvements can be made, these are all belonged to the scope of protection of the present invention.
Claims (15)
1. a kind of sealer with compression, is used for angiocarpy bracket, the sealer setting is propped up in angiocarpy
The surface of the basis material of frame, which is characterized in that its corrosion rate is lower than the corrosion rate of basis material, the sealer
Prestressing force with pressure.
2. a kind of sealer with compression according to claim 1, which is characterized in that the sealer
Material be one of metal, metal oxide, inorganic compound or organic polymer or several.
3. a kind of sealer with compression according to claim 1, which is characterized in that the performance coating is
One or more layers.
4. the matrix material of angiocarpy bracket is arranged in a kind of manufacturing method of the sealer with compression, sealer
The surface of material, which is characterized in that the sealer is coated and introduces compression during generating.
5. a kind of manufacturing method of sealer with compression according to claim 4, which is characterized in that applying
In the technical process for applying and generating protective layer, basis material is made to be in the state being mechanically stretched, applies and generate protective layer
After technical process, the mechanical tensile forces of basis material are discharged, so that generating compression in protective layer.
6. a kind of manufacturing method of sealer with compression according to claim 5, which is characterized in that described
Protective layer is zinc layers or zinc alloy layer, and described matrix material is magnesium or magnesium alloy；Coating and the technique for generating protective layer are as follows: in magnesium
Or the surface of the angiocarpy bracket of magnesium alloy materials carries out coating zinc layers or galvanized alloy layer by plating mode.
7. a kind of manufacturing method of sealer with compression according to claim 5, which is characterized in that described
Protective layer is magnesium oxide layer, and described matrix material is magnesium or magnesium alloy；Coating and the technique for generating protective layer are as follows: use hydrofluoric acid
The surface of the middle angiocarpy bracket for impregnating magnesium or magnesium alloy materials is to generate magnesium oxide layer.
8. a kind of manufacturing method of sealer with compression according to claim 4, which is characterized in that first
The basis material of metal material is heated to high temperature, applies and generates at high temperature and protect solution ceramics；Then ring is cooled the temperature to
Border temperature generates compression in ceramic protective layer since the thermal expansion coefficient of metal is greater than the thermal expansion coefficient of ceramics.
9. a kind of manufacturing method of sealer with compression according to claim 4, which is characterized in that first
First, at ambient temperature, bio-vitric is applied on the surface of basis material using sol-gal process；It is then heated to high temperature, is burnt
Knot a few hours generate the bio-vitric layer in fine and close and few cavity；It is cooled to environment temperature, due to the thermal expansion coefficient of basis material
Greater than bio-vitric thermal expansion coefficient, extrusion stress is generated in bio-vitric layer.
10. a kind of manufacturing method of sealer with compression according to claim 4, which is characterized in that first
First, hydroxyapatite is applied on the surface of basis material using slurry coating method；It is then heated to 500-600 °C, is sintered a few hours
Generate the hydroxyapatite layer in fine and close and few cavity；It is cooled to environment temperature, since the thermal expansion coefficient of basis material is greater than hydroxyl phosphorus
Lime stone, hydroxyapatite layer is interior to generate extrusion stress.
11. a kind of manufacturing method of sealer with compression according to claim 4, which is characterized in that
The surface of basis material is generated using the 0.01-5 micron little particle of ion injection method injection other materials and is squeezed prestressing force.
12. a kind of manufacturing method of sealer with compression according to claim 11, which is characterized in that when
Using magnesium or when being used as basis material of magnesium alloy, the little particle of the other materials of injection is potassium particle, calcium particle or sodium particle
One of or it is several.
13. a kind of manufacturing method of the sealer with compression, which is characterized in that after the sealer is coated
Introduce compression.
14. a kind of manufacturing method of sealer with compression according to claim 13, which is characterized in that first
First, by the basis material of surface coating organic polymer；Then slow stretching at a temperature of medium temperature, basis material generate elasticity and become
Shape, and organic polymer generates Creep Plastic deformation；When elongation strain < 0.2%, it is cooled to environment temperature or low temperature, then rapidly
Pulling force is discharged, basis material and organic polymer generate elastical retraction simultaneously, since organic polymer is in medium temperature slow stretching mistake
The Creep Plastic deformation generated in journey, for organic polymer coating after low temperature rapidly elastic recovery, inside generates extrusion stress.
15. a kind of angiocarpy bracket, which is characterized in that its surface is arranged just like sealer described in claim 1-14.
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