CN107354335A - A kind of method and apparatus for preparing bio-medical open celled foam Zinc material - Google Patents
A kind of method and apparatus for preparing bio-medical open celled foam Zinc material Download PDFInfo
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- CN107354335A CN107354335A CN201710576560.5A CN201710576560A CN107354335A CN 107354335 A CN107354335 A CN 107354335A CN 201710576560 A CN201710576560 A CN 201710576560A CN 107354335 A CN107354335 A CN 107354335A
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- calcium chloride
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
- C22C1/081—Casting porous metals into porous preform skeleton without foaming
- C22C1/082—Casting porous metals into porous preform skeleton without foaming with removal of the preform
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/08—Methods for forming porous structures using a negative form which is filled and then removed by pyrolysis or dissolution
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The present invention relates to a kind of method and device for being used to prepare bio-medical open celled foam Zinc material, its method comprises the following steps：The spherical calcium chloride granules of uniform particle sizes are sintered first, obtain calcium chloride precast body；Metallic zinc is placed on calcium chloride precast body, is placed in heat temperature raising in vacuum seepage device, while opens vavuum pump and vacuum valve vacuumizes；After complete fluid-tight, vavuum pump and vacuum valve are closed；It is incubated after seepage flow temperature is reached, opens pressurization valve afterwards and carry out Seepage Foundry, obtain zinc calcium chloride complex；After body solidification to be composite, with water-soluble removing calcium chloride granules, that is, open celled foam Zinc material is obtained.Open celled foam Zinc material even pore distribution prepared by this method, adjustable porosity, aperture size and its distribution are controllable, and connectivity is good between hole, while can prepare the open celled foam Zinc material with gradient-structure, suitable for bone tissue engineering stent material.The present invention device solve existing apparatus seepage flow deficiency, seepage flow excessively etc. technical problem.
Description
Technical field
The invention belongs to technical field of biological medical material preparation, and in particular to one kind is used to prepare bio-medical perforate bubble
The method and apparatus of foam Zinc material.
Background technology
Medical metal material has been widely used as human body hard tissue reparation and alternate material.But clinical research
It was found that the modulus of elasticity of medical metal material and bone mismatches, " stress shielding " phenomenon is produced after implantation, causes the pine of implant
Dynamic or fracture.Secondly, although some medical metal materials have good biocompatibility, they still fall within biologically inert material
Material, is difficult to form direct combination with sclerous tissues after implantation, easily loosens, cause graft failure.In order to solve above-mentioned ask
Topic, scholars propose the method that hole is introduced in medical metal material, are made into porous metal material.The presence of hole
There is the improvement of the following aspects to the performance of material：Density, intensity and the modulus of elasticity of porous metal material can be by right
The adjustment of pore size and porosity is compatible to reach biomethanics, so as to which stress shielding phenomenon is mitigated or eliminated；Also,
Distinctive loose structure and coarse surfaces externally and internally are advantageous to sticking for Gegenbaur's cell breed and break up, and promote new bone tissue to grow into
Hole, make implant with forming biological fixation between bone；In addition, the pore structure of three-dimensional communication can make body fluid and nutriment exist
Transmitted in implant, promotion organization regeneration and reconstruction, accelerate agglutination.
At present, can mainly there are porous Ti and Ti alloys, porous tantalum as bone tissue reparation and the porous metal material replaced
Deng.But human body is simply temporary transient in some cases to the functional requirement of metal material implant, such as orthopedic steel plate, screw material
Material, intravascular stent etc., generally require the taking-up of row second operation.In addition, metal implant deposits implantation bone for a long time can produce stress
Occlusion effect, influence bone growth and development.In view of the foregoing, in recent years, domestic and international researcher is to medical degradable metal
Material is researched and developed, and the research for degradable metal biomaterial at present is concentrated mainly on magnesium and magnesium alloy, but magnesium
Degradation rate is very fast in human body, it tends to be difficult to reaches requirement.Similar with mechanism of degradation in degradable magnesium alloy body, zinc and zinc close
Gold can also degrade in vivo, and for magnesium and its alloy, zinc and kirsite degradation rate are relatively slow, can be in body
It is interior to play sufficiently long time, it is preferably as needing the relatively low bone tissue engineering stent material of degradation rate, thus turn into most
Near study hotspot, but the foam metal prepared using conventional method is generally polygonal holes, hole it is in irregular shape, make
Its use is restricted.
For porous metal material, preparation method determines its loose structure, and then have impact on other performances.Sintering process is wide
The general preparation applied to porous metal material, this technology have the shortcomings that obvious：Pore structure connectivity is poor；Porosity is universal
It is relatively low；Scantling and shape are limited by Preparation equipment.By contrast, infiltration casting is by " anti-to precast body
To duplication " and required open cell foam metal is obtained, it can be realized by changing prefabricated preparation process to open cell foam metal
Shape, size and its control of distribution of hole, preparation technology is easy flexibly, and the porous metal material pore structure of acquisition is equal
Even, connectivity is good.But there is seepage flow deficiency, seepage flow and excessively and the defects of central defect etc. is intrinsic ask in traditional infiltration casting
Topic, and generally from Nacl sodium chloride particle as precast body agglomerated material, the porous metal material hole finally obtained
For polygonal, its internal structure is extremely complex, and the reproducibility and repeatability of performance are bad；And porous metal material hole
It is connective bad, it is easy to form closed pore defect, cause the sodium chloride particle in hole not dissolve, it can be produced for a long time
Raw serious corrosion, the final quality for influenceing material.
In addition, the contradiction how solved between the mechanical properties such as porosity and compression strength turns into bio-medical metal material
Expect the important directions of research.At present, solving the method for this contradiction mainly has two classes, and one kind is by changing its composition, is such as led to
Addition rare earth is crossed to improve mechanical property.Another kind of is exactly to pass through geometry reasonable in design, has gradient knot by preparing
The porous metals of structure realize, such as forming shape method using Laser Near, to prepare the POROUS TITANIUM with gradient porosity to reduce its firm
Degree, reaches the modulus of elasticity to match with mankind's cortex bone.But its hole lateral direction penetrating processed is poor, and hole wall
Without micropore, it is unfavorable for the combination of material and bone tissue.Some scholars realize ladder by way of orienting freezing casting shaping
Structure is spent, obtains outside loose, the gradient porous titanium of interior solid, however, POROUS TITANIUM aperture prepared by this method is too small, and work
Skill is complicated, and efficiency is low.
The content of the invention
(1) technical problems to be solved
In order to solve the above mentioned problem of prior art, the present invention provides a kind of for preparing bio-medical open celled foam zinc material
The method and device of material, open celled foam Zinc material prepared by methods described, which can be used as, is used for bone tissue engineering stent material, its hole
Gap is evenly distributed, adjustable porosity, and aperture size and its distribution are controllable, and connectivity is good between hole, and its device solves existing dress
It is insufficient to put seepage flow, the technical problems such as seepage flow is excessive.
(2) technical scheme
In order to achieve the above object, the main technical schemes that the present invention uses include：
A kind of method for preparing bio-medical open celled foam Zinc material, comprise the following steps：
S1, spherical calcium chloride granules are taken, sinter bonded prepares an open-pored porous calcium chloride precast body；
S2, the step S1 calcium chloride precast bodies obtained are placed in sealing device, metallic zinc or kirsite are covered
In on the calcium chloride precast body, internal vacuum maintains -0.09~-0.098MPa, gradually heating make the metallic zinc and
Zinc alloy material is melted；
S3, after molten metal zinc or kirsite realize complete fluid-tight on precast body top, close vacuum；
S4,550 DEG C~650 DEG C be incubated 10 minutes~30 minutes, to the sealing device internal pressurization, in seepage pressure
Lower carry out Seepage Foundry, zinc-calcium chloride complex is formed after seepage flow；
S5, after the solidification of the zinc-calcium chloride complex, remove spherical calcium chloride granules, obtain spherical pore open celled foam
Zinc.
Preparation method as described above, it is preferable that in the step S1 particle diameter of spherical calcium chloride granules be 0.3mm~
5.0mm。
Method as described above, it is preferable that sinter bonded prepares an open-pored porous calcium chloride precast body in the step S1
Including：The calcium chloride granules are attached in mould, apply pressure, heat-agglomerating, the sintering on the calcium chloride granules
Temperature is 600 DEG C~720 DEG C, and the sintering time is 2 hours~10 hours, and furnace cooling afterwards obtains open-pored porous calcium chloride
Precast body.
Wherein, sintering time and the pressure applied can be depending on the requirements to product porosity, and mould can use corundum
Crucible, the pressure applied on calcium chloride granules are 0.1kg~0.8kg weight pressure, and particle is bigger, and ballast is bigger.
Method as described above, it is preferable that the calcium chloride granules layering of different-grain diameter is attached to mould in the step S1
It is interior, prepare the open-pored porous calcium chloride precast body with gradient-structure.
Method as described above, it is preferable that in the step S4, sealing device internal pressurization is pressurizeed with inert gas,
The seepage pressure is 0.1Mpa~1.0Mpa.
Method as described above, it is preferable that the sealing device in the step S2 includes resistance-heated furnace, airway tube, use
In the mould and casting chamber that prepare porous material, wherein, the casting chamber is placed in the cavity of the resistance-heated furnace, described to lead
Tracheae is the pipeline of T-shaped connection, and its lower end connects the casting chamber, the left and right of the airway tube through the resistance-heated furnace
Both ends are connected to inert gas bomb and vavuum pump；The mould for being used to prepare porous material is placed in the casting chamber
Interior, the inert gas bomb and vavuum pump are equipped with pressure gauge.
Further, the casting chamber includes casting chamber's cover and casting chamber's barrel, casting chamber's cover and casting chamber's cylinder
Connection is bolted between wall, the lower end of the airway tube connects casting chamber's cover, casting chamber's cover and casting
Seal washer is provided between the barrel of room, one end close to the inert gas bomb on the airway tube is provided with pressurizing valve
Door, the other end close to the vavuum pump are provided with vacuum valve.
A kind of device for being used to prepare bio-medical open cell foam metal material, it includes resistance-heated furnace, airway tube, use
In the mould and casting chamber that prepare porous material, wherein, the casting chamber is placed in the cavity of the resistance-heated furnace, described to lead
Tracheae is the pipeline of T-shaped connection, and its lower end connects the casting chamber, the left and right of the airway tube through the resistance-heated furnace
Both ends are connected to inert gas bomb and vavuum pump；The mould for being used to prepare porous material is placed in the casting chamber
Interior, the inert gas bomb and vavuum pump are equipped with pressure gauge.
Device as described above, it is preferable that the casting chamber includes casting chamber's cover and casting chamber's barrel, the casting chamber
Connection is bolted between cover and casting chamber's barrel, the lower end of the airway tube connects casting chamber's cover, the casting
Make and seal washer is provided between room cover and casting chamber's barrel.
Device as described above, it is preferable that one end close to the inert gas bomb on the airway tube is provided with
Pressurization valve, the other end close to the vavuum pump are provided with vacuum valve.
Device as described above, it is preferable that the resistance-heated furnace includes uniformly adding towards casting chamber's barrel periphery
The heater of heat.
Device as described above, it is preferable that the heater includes a plurality of along casting chamber's barrel axial direction uniform intervals cloth
The circular heating elements put, or including a spiral shape heating element heater being evenly arranged around casting chamber's barrel.
(3) beneficial effect
The beneficial effects of the invention are as follows：
1. the preparation method of the present invention, technique is simple, easy to operate, solves and seepage flow in existing conventional method be present not
Foot, seepage flow are excessively and the technological deficiency problem such as central defect.The open celled foam Zinc material hole shape prepared using the inventive method
To be spherical, performance repeatability and repeatability it is good, no closed pore defect, hole it is connective good, aperture size and its distribution can
Control.
2. the present invention prepares the perforate chlorine with three-dimensional communicating structure using calcium chloride granules by high temperature sintering mode
Change calcium precast body, then using vacuum pressed seepage flow mode to ensure that molten metal is filled up completely with precast body multiple so as to obtain zinc-calcium chloride
It is fit.Therefore, the architectural feature of the precast body has just been directly becoming the pore character of open celled foam Zinc material.
3. the present invention can by choosing various sizes of calcium chloride granules, using different sintering temperatures and time and
Regulating and controlling the pore character of perforate calcium chloride precast body using different ballasts, final acquisition aperture size and its distribution are controllable,
Even pore distribution, adjustable porosity, the good open celled foam Zinc material of connectivity between hole.
4. the present invention can be prepared with gradient knot by the way of the spherical calcium chloride granules of different-grain diameter are sequentially accumulated
The open-pored porous calcium chloride precast body of structure, may finally prepare the open celled foam zinc with gradient-structure, its pore size can
Into arrangement of gradients, its rigidity, while porosity needed for guarantee are reduced, effectively improves material property.
5. the spherical calcium chloride that the present invention uses is a kind of industrial product, cost is cheap, is commonly used for drier and road melts
Ice agent.Solubility of the calcium chloride in water is 74.5g at 20 DEG C, (is at 20 DEG C much larger than solubility of the sodium chloride in water
36g), compared with the sodium chloride that conventional method uses, calcium chloride it is final it is water-soluble during be easier to dissolve, be not easy to be formed residual
Stay, improve production efficiency and product quality.
6. bio-medical open celled foam Zinc material biocompatibility prepared by the present invention is excellent, the power of open celled foam Zinc material
Learn performance with people's biomechanics of bone performance to match, and the open-celled structure of three-dimensional communication can make body fluid and nutriment in implant
Middle transmission, promotion organization regeneration and reconstruction, accelerate agglutination.
7. the device provided by the present invention for preparing bio-medical open cell foam metal material, efficiently solves existing ooze
The defects of seepage flow that device occurs is insufficient, seepage flow is excessive or preparation process is unmanageable is flowed, the simple processing stage of its device is low, just
In manufacture, cost is low, and use is simple to operate, convenient, it is not necessary to which that higher technical staff can be operated.
Brief description of the drawings
Fig. 1 is the profile of the preferably vacuum seepage device of the present invention one；
Fig. 2 is the result figure of the open celled foam Zinc material prepared in the present invention in embodiment 3-5；
Fig. 3 is the open celled foam zinc material scanning electron microscope (SEM) photograph prepared in the present invention in embodiment 3；
Fig. 4 is the foam zinc compression stress strain curve figure of the different porosities obtained in the present invention in embodiment 4；
Fig. 5 is the result figure of the open celled foam Zinc material prepared in the present invention in embodiment 6.
【Description of reference numerals】
1：Resistance-heated furnace；
2：For preparing the mould of porous material；
3：Airway tube；
4：Cover；
5：Barrel；
6：Bolt；
7：Pressurization valve；
8：Vacuum valve；
9：Precast body；
10：Metallic zinc；
1-1：Heating element heater.
Embodiment
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by embodiment, to this hair
It is bright to be described in detail, wherein, described method and the non-special declaration of reagent are using conventional method in the art and commercially available
Reagent.
Embodiment 1
The vacuum seepage device designed in the present invention, available for open cell foam metal material is prepared, its structural representation is such as
Shown in Fig. 1, including resistance-heated furnace 1, casting chamber, the mould 2 for preparing porous material, airway tube 3, wherein, casting chamber puts
In in the cavity of resistance-heated furnace 1, casting chamber includes cover 4 and barrel 5, is fixedly connected between cover 4 and barrel 5 by bolt 6,
Airway tube 3 is the pipeline of T-shaped connection, and its lower end connects casting chamber, the left and right ends difference of airway tube through resistance-heated furnace 1
It is connected with the inert gas bomb for providing seepage pressure for casting chamber and the vavuum pump for vacuum extractor；It will be used for
The mould for preparing porous material is placed in casting chamber, and pressure gauge is provided with inert gas bomb gas outlet, can also be lazy
Pressure gauge is provided between property gas high pressure bottle and mozzle, for controlling seepage pressure；Inert gas bomb is in casting chamber
A kind of seepage pressure of inert gas is provided, vavuum pump is that offer subnormal ambient, its vavuum pump carry pressure gauge in casting chamber, is used
The vacuum of environment is taken out in display.
It is high close to inert gas on airway tube 3 in order to further be easy to control seepage pressure and vacuum in casting chamber
One end of pressure bottle is provided with pressurization valve 7, and when opening pressurization valve 7, inert gas bomb can will be casting with being connected in casting chamber
Make room and seepage pressure is provided, the metallic solution for being advantageously used for preparing the mould of porous material is penetrated into precast body；In airway tube 3
The upper other end close to vavuum pump is provided with vacuum valve 8.The setting of pressurization valve 7 and vacuum valve 8 makes in casting chamber added with oozing
Flowing pressure and it can be formed and vacuumize closed cavity, the seepage pressure in casting chamber and vacuum is effectively ensured.
Resistance-heated furnace can be the heater uniformly heated towards casting chamber's barrel periphery, further, heating
Device is a plurality of circular heating elements 1-1 arranged along casting chamber's barrel axial direction uniform intervals, and heater can also be set to one
The spiral shape heating element heater being evenly arranged around casting chamber's barrel, heating element heater can electric furnace heating wire or circuit bars.A plurality of annular-heating
Element or spiral shape heating element heater make homogeneous heating in casting chamber, and metal derby fusing is effectively ensured.
The shape of porous material required for mould for preparing porous material can be made as needed, design the shape of mould
Shape.The mould used in the application uses corundum crucible, and vacuum seepage device of the invention is before use, as shown in fig. 1, incite somebody to action
Precast body 9 be placed in will be placed in the mould for preparing porous material, above precast body metallic zinc 10 or zinc alloy material or its
Its metal material, corundum crucible is placed in casting chamber's barrel 5, covers cover 4, barrel 5 and cover are fixedly connected with using bolt 6
4, in order that the sealing in casting chamber is more superior, seal washer is additionally provided between barrel and cover, seal washer is copper packing
Circle.Wherein, barrel material, cover material and airway tube are heat-resistance stainless steel or 45# Steel materials, the lower end of airway tube and cover
It is to be welded directly together, the both ends of airway tube are to use stainless steel screw thread with the connection of vavuum pump and inert gas bomb respectively
Pipe connects, and vavuum pump and inert gas bomb are respectively provided with pressure gauge, is cast for measuring vacuum in casting chamber with entering
The pressure of room inert gas；Wherein, vavuum pump can be vacuumized using rattan original vavuum pump work station, inert gas bomb
Inert gas can use nitrogen or argon gas bomb etc..
The precast body being typically prepared is the complicated casting mold with porous capillary structure.If according to conventional articulated gravity casting process,
In pore of the molten metal between filler particles during seepage flow, due to surface tension of liquid, molten metal and die surface and molten metal
The presence of friction between inside can produce larger mold filling resistance, only be difficult to fill type by Action of Gravity Field complete.Properly increase and ooze
Temperature is flowed to improve the mobility of molten metal, or the mold-filling capacity of molten metal can be improved by way of the seepage flow that pressurizes, but
If a large amount of gases in casting mold be present can not discharge, it can not still realize and preferably fill type effect.Therefore during Seepage Foundry,
Keep being in negative pressure state inside precast body, be to ensure the necessary condition that cavity filling process can be smoothed out, only certain
Under negative pressure, zinc liquid could be penetrated into smoothly in multi-hole casting, the final open celled foam zinc for obtaining structural integrity.Vacuum is not only
Can type is filled in influence be smoothed out, and also contribute to the Forming Quality and parameter of pore structure of final foam zinc.The present inventor passes through
Lot of experiments finds that vacuum can influence the porosity and through-hole rate size of the metal material prepared, because vacuum is big
The small full level that can influence molten metal hole between precast body particle, vacuum is bigger, and full level is bigger, porosity and
Through-hole rate all reduces therewith, and vice versa.In addition, the size of vacuum affects the speed of molten metal seepage flow.Too low vacuum
Degree is too small to filling type booster action, and percolation flow velocity is relatively low, may have influence on the integrality for filling type.It is and excessive, it is equally possible to occur
Type situation is overcharged, equally cannot get complete material.It is -0.090MPa~-0.098MPa that vacuum is selected in the present invention.
Traditional Seepage Foundry is prepared in open cell foam metal technique, and its negative pressure of vacuum is that the effect of liter liquid (is made in negative pressure
Melt is set to run from the bottom up under), there are various defects in the improper sample for easily to prepare of vacuum degree control, works as vacuum
Easily there is seepage flow deficiency in degree selection when too small, vacuum selection the defects of seepage flow is excessive easily occurs when excessive.And the present invention
Device is different from vacuum seepage device in the prior art, and also different using principle, apparatus of the present invention are prepared out in use
During the foam metal material of hole, first vacuumized, the air in precast body is all discharged, precast body is in negative pressure state, it
After carry out heating fusing metal material, in same container, molten metal liquation makes precast body complete for metal material and precast body
All standing, it is exactly by the complete fluid-tight of precast body, is that seepage pressure action metals melt in precast body internal negative pressure, and in impressed pressure
Liquid is penetrated into precast body, can fully penetrate into molten metal and Seepage Foundry is carried out in precast body.Avoid the occurrence of seepage flow deficiency, seepage flow
Excessively and there is the defects of crystallization centre, it is seen then that vacuum seepage casting device of the invention can effectively solve prior art
The technical problem for the defects of middle seepage flow deficiency, seepage flow are excessively and central defect etc. is intrinsic.
The use of the vacuum seepage device of the present invention can be directly used for the sintering of precast body, and spherical calcium chloride granules are attached to
In mould, pressurizeed on particle plus weight, barrel and cover are tightly connected with bolt, close mozzle top or so
The pressurization valve and vacuum valve at both ends, the door of resistance-heated furnace is closed, carry out heat-agglomerating；It is cold with stove after sintering is completed
But open-pored porous calcium chloride precast body is obtained, opens the door of resistance-heated furnace, bolt is opened and removes cover, remove weight, put
Enter metallic zinc or zinc alloy material or other metal materials on precast body, then sealed cylinder and cover with bolt and copper washer
Connection, with stainless steel screwed tube airway tube left and right ends respectively with the vavuum pump of pumped vacuum systems and the indifferent gas of compression system
Body bomb connects.Finally place into and vacuum seepage is carried out in resistance-heated furnace；After completing vacuum seepage, after furnace cooling,
First vavuum pump and inert gas bomb are disassembled, then opens pressurization valve or vacuum valve and is let out with air communication
Pressure.
Embodiment 2
Bio-medical open celled foam Zinc material is prepared, using the vacuum seepage device described in embodiment 1, specific preparation side
Method comprises the following steps：
(1), screen cloth of the spherical calcium chloride through different pore size is sieved, chooses the spherical calcium chloride that particle diameter is 0.5mm
Particle is stand-by；
(2), the spherical calcium chloride granules of above-mentioned particle diameter are attached in mould, heat-agglomerating, sintering temperature is 600 DEG C, permanent
Warm sintering time is 2 hours, while applies 0.1kg pressure on particle, and furnace cooling afterwards obtains open-pored porous calcium chloride
Precast body；
Wherein, applying pressure on particle is determined according to the requirement of the required product porosity prepared；
(3), metallic zinc or zinc alloy material are placed on precast body, vacuum seepage device is assembled and covers cover,
Fastened with bolt, close pressurization valve and vacuum valve and sealed, heat temperature raising, while open vavuum pump and vacuum valve is taken out
Vacuum makes internal vacuum maintain -0.09~-0.098MPa；
(4), heating is completely melt metallic zinc and zinc alloy material, and it is complete to treat that molten metal bath is realized on precast body top
After fluid-tight, vavuum pump and vacuum valve are closed；
Drawn according to the experience of many experiments：Because the fusing point of zinc is 420 DEG C or so, so being slowly warming up to 500-550 DEG C
When think that fluid-tight is realized in Zinc material fusing, that is, fast can when reaching seepage flow temperature closes vacuum；If using different
Zinc alloy material, also just work as and be warming up to seepage flow temperature i.e. it is believed that zinc alloy material is completely melt, and molten metal bath is prefabricated
Also complete fluid-tight is realized in body top, so that it may close vavuum pump and vacuum valve；
(5) 10~30 minutes, are incubated after 650 DEG C of seepage flow temperature is reached, then opens pressurization valve, opens inert gas
Bomb, it is 1.0MPa to make seepage pressure, carries out Seepage Foundry, is pressurizeed after seepage flow 5min, i.e., seepage flow finishes, and closes pressurizing valve
Door, form zinc-calcium chloride complex；
(6), after body solidification to be composite, spherical calcium chloride granules is removed with water-soluble, that is, obtain spherical pore open celled foam zinc.
Embodiment 3
It is with the difference of embodiment 2, (1) chooses the spherical calcium chloride that particle diameter is 2mm；(2) sintering temperature is
650 DEG C, the Isothermal sinter time is 4 hours, applies the weight pressure that pressure is 0.3kg；(5) 620 DEG C of seepage flow temperature, seepage pressure
For 0.7Mpa.
Embodiment 4
It is with the difference of embodiment 2, (1) chooses the spherical calcium chloride that particle diameter is 3mm；(2) sintering temperature is
670 DEG C, the Isothermal sinter time is 6 hours, applies the weight pressure that pressure is 0.5kg；(5) 600 DEG C of seepage flow temperature, seepage pressure
For 0.5Mpa.
Embodiment 5
It is with the difference of embodiment 2, (1) chooses the spherical calcium chloride that particle diameter is 4mm；(2) sintering temperature is
700 DEG C, the Isothermal sinter time is 7 hours, applies the weight pressure that pressure is 0.8kg；(5) 570 DEG C of seepage flow temperature, seepage pressure
For 0.3Mpa.
Embodiment 3-5 is tested three times respectively, to being measured for the open celled foam zinc of acquisition, specifically in an experiment
Sample warp is cut into 40 × 30mm of Φ cylinder, (measure porous metals sample arranges water based on hydrostatics method
The solid volume and the closed pore volume sum (aperture portion that water can be filled up in porous metals sample of volume, as porous metals
Point)), the open-cell porosity of measurement porous metals sample；Using the method for direct measurement volume and quality measure porous sample
Overall porosity.Specific computation model is as follows：
Open-cell porosity：Overall porosity：
In formula：M --- it is the quality (g) of sample；ν --- it is the apparent volume (cm of sample3)；
ρ --- it is the density (g/cm of metal3)；νIt is real+to close--- it is solid volume and closed pore volume sum (cm3)；
The compression performance test of porous material is carried out on Instron5843 type universal testing machines, and loading velocity is
1mm/min, test temperature are room temperature.
The measurement result of physical parameter is shown in Table 1, and the measurement result of compression performance parameter is shown in Table 2, wherein numbering is 1-1,1-
2nd, 1-3 is respectively the parallel test of embodiment 3, and numbering 2-1,2-2,2-3 are respectively the parallel test of embodiment 4, and numbering is
3-1,3-2,3-3 are respectively the parallel test of embodiment 5.
The physical parameter of open celled foam Zinc material obtained in the embodiment 3-5 of table 1
For the porosity of open celled foam zinc prepared by the present invention between 59%~70%, the porosity of cancellous bone is about 40%
~90%, it can be seen that the porosity and the porosity of skeleton cancellous bone of opening porous zinc prepared by vacuum seepage casting
It is higher with degree, and the requirement of privileged site bone porosity can also be reached by the adjustment to technological parameter.As especially
It is high for 1-3,2-3,3-3 this three groups open-cell porosity, hole it is connective good, closed pore defect is considerably less.
The compression performance parameter of the open celled foam Zinc material of table 2
The above results illustrate the modulus of elasticity of the open celled foam Zinc material in three kinds of apertures be divided into 0.4GPa~0.7GPa,
Between 0.5GPa~0.9GPa and 1.6GPa~2.1GPa, compression strength be respectively 6.3MPa~8.6MPa, 6.7MPa~
Between 13.0MPa and 11.3MPa~14.8MPa, higher than the compression strength of people's cancellous bone bone, the springform of modulus of elasticity and people's bone
Amount matches, and meeting the requirement of cancellous bone, (compression strength of people's cancellous bone bone is 0.3MPa~1.5MPa, modulus of elasticity 1GPa
~2GPa).
The open celled foam Zinc material prepared to embodiment 3-5, as a result as shown in Fig. 2 wherein A, B, C are respectively embodiment 3-
The top view of the 5 open celled foam Zinc materials prepared, a, b, c are respectively the solid of open celled foam Zinc material prepared by embodiment 3-5
Figure, it can also be seen that aperture is respectively 2.0mm, 3.0mm, 4.0mm from figure, even pore distribution, connectivity is good between hole, hole
It can be adjusted according to the size of calcium chloride granules particle diameter, porosity can be adjusted according to the technology of preparing of precast body, such as be used
The size of institute's ballast is adjusted.
Wherein, the pore structure of the open celled foam Zinc material prepared to embodiment 3 carries out electron-microscope scanning analysis, its SEM photograph
As shown in figure 3, as can be seen from the figure pore communication is preferable, porosity and open-cell porosity are higher, and mechanical property is also preferable.
For the foam zinc compression stress that aperture in embodiment 4 is these three different voidages of 3.0mm 3-1,3-2,3-3
For strain curve as shown in figure 4, wherein abscissa is strain, ordinate is stress, it can be seen that the foam zinc prepared is in
Now typical plastic foam feature.
Embodiment 6
It is with the difference of embodiment 2, (1) chooses particle diameter respectively in 4mm, 3mm, 2mm spherical calcium chloride；
(2) the spherical calcium chloride granules that a certain amount of particle diameter is 4mm are attached to as bottom in mould, then loaded on bottom a certain amount of
Particle diameter be 3mm spherical calcium chloride granules be used as intermediate layer, finally a certain amount of particle diameter is mounted in for 2mm spherical calcium chloride
Top layer is used as above intermediate layer；Sintering temperature is 680 DEG C, and the Isothermal sinter time is 5 hours, applies the weight that pressure is 0.6kg
Pressure；(5) 620 DEG C of seepage flow temperature, seepage pressure 0.7Mpa；(6) the spherical pore open celled foam zinc with gradient-structure is obtained,
Pore size is into arrangement of gradients, and as a result as shown in figure 5, top layer aperture is 2.0mm, intermediate layer aperture is 3.0mm, and bottom aperture is
4.0mm, improve material property.
Embodiment 7
The present embodiment is that to prepare the aperture of open celled foam Zinc material be 5mm, specific method be different from embodiment 2 be：
(1) the spherical calcium chloride that particle diameter is 5mm is chosen；(2) sintering temperature is 720 DEG C, and the Isothermal sinter time is 10 hours, applies pressure
Power is 0.8kg weight pressure；(5) 550 DEG C of seepage flow temperature, seepage pressure 0.1Mpa.
The above described is only a preferred embodiment of the present invention, being not the limitation that other forms are done to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
- A kind of 1. method for preparing bio-medical open celled foam Zinc material, it is characterised in that comprise the following steps：S1, spherical calcium chloride granules are taken, sinter bonded prepares an open-pored porous calcium chloride precast body；S2, the step S1 calcium chloride precast bodies obtained are placed in sealing device, metallic zinc or kirsite are placed in described On calcium chloride precast body, internal vacuum maintains -0.09~-0.098MPa, and gradually heating makes the metallic zinc and kirsite Material melts；S3, after molten metal zinc or kirsite realize complete fluid-tight on the calcium chloride precast body top, close vacuum；S4,550 DEG C~650 DEG C be incubated 10 minutes~30 minutes, the sealing device internal pressurization is entered under seepage pressure Row Seepage Foundry, zinc-calcium chloride complex is formed after seepage flow；S5, after the solidification of the zinc-calcium chloride complex, remove spherical calcium chloride granules, obtain spherical pore open celled foam zinc.
- 2. the method as described in claim 1, it is characterised in that the particle diameter of spherical calcium chloride granules is in the step S1 0.3mm~5.0mm.
- 3. the method as described in claim 1, it is characterised in that sinter bonded prepares an open-pored porous chlorination in the step S1 Calcium precast body includes：The calcium chloride granules are attached in mould, apply pressure on the calcium chloride granules, heat-agglomerating, The sintering temperature is 600 DEG C~720 DEG C, and the sintering time is 2 hours~10 hours, and it is more to obtain perforate for furnace cooling afterwards Hole calcium chloride precast body.
- 4. method as claimed in claim 3, it is characterised in that be layered the calcium chloride granules of different-grain diameter in the step S1 It is attached in mould, prepares the open-pored porous calcium chloride precast body with gradient-structure.
- 5. method as claimed in claim 3, it is characterised in that in the step S4, to sealing device internal pressurization inertia Gas pressurized, the seepage pressure are 0.1Mpa~1.0Mpa.
- 6. a kind of be used to prepare the device of bio-medical open cell foam metal material, it is characterised in that it include resistance-heated furnace, Airway tube, the mould for preparing porous material and casting chamber, wherein, the casting chamber is placed in the cavity of the resistance-heated furnace Interior, the airway tube is the pipeline of T-shaped connection, and its lower end connects the casting chamber through the resistance-heated furnace, described to lead The left and right ends of tracheae are connected to inert gas bomb and vavuum pump；The mould for being used to prepare porous material is placed in In the casting chamber, the inert gas bomb and vavuum pump are equipped with pressure gauge.
- 7. device as claimed in claim 6, it is characterised in that the casting chamber includes casting chamber's cover and casting chamber's barrel, Connection is bolted between casting chamber's cover and casting chamber's barrel, the lower end of the airway tube connects casting chamber's cylinder Lid, seal washer is provided between casting chamber's cover and casting chamber's barrel.
- 8. device as claimed in claim 6, it is characterised in that close to the inert gas bomb on the airway tube One end is provided with pressurization valve, and the other end close to the vavuum pump is provided with vacuum valve.
- 9. device as claimed in claim 6, it is characterised in that the resistance-heated furnace is included towards outside casting chamber's barrel The heater that week uniformly heats.
- 10. device as claimed in claim 9, it is characterised in that the heater includes a plurality of along casting chamber's barrel axial direction The circular heating elements of uniform intervals arrangement, or including a spiral shape heating unit being evenly arranged around casting chamber's barrel Part.
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