CN103643263A - Metal-based structural member with shark placoid scale structure and preparation method of metal-based structural member - Google Patents
Metal-based structural member with shark placoid scale structure and preparation method of metal-based structural member Download PDFInfo
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Abstract
The invention provides a metal-based structural member with a shark placoid scale structure and a preparation method of the metal-based structural member. The preparation method comprises the following steps of preparing a biological template of a shark placoid scale; preparing a negative ceramic template of the shark placoid scale; preparing the metal-based structural member with the shark placoid scale structure. The negative ceramic template of the shark placoid scale is prepared through the steps of preparing a premixed solution; preparing ceramic slurry; carrying out injection molding on a ceramic gel; carrying out gradient dewatering and drying on the ceramic gel; demolding the biological template of the shark placoid scale; sintering a ceramic blank of the shark placoid scale. The metal-based structural member with the shark placoid scale structure is prepared through the steps of spraying a welding stopping agent; adding metal-based powder; covering, welding and packaging; carrying out vibration packing and vacuum leak detection; sintering the metal-based powder; demolding the metal-based structural member. The metal-based structural member with the shark placoid scale structure, provided by the invention, is prepared by using the method. The preparation method provided by the invention can be used for realizing the preparation of a metal material with the shark placoid scale structure and overcoming various defects of a nonmetallic material.
Description
Technical field
The present invention relates to a kind of metal matrix component with shark placoid scale structure and preparation method thereof, belong to metal forming technical field.
Background technology
Shark body surface is covered by the placoid scale (placoid scales) of diamond array, presents the surface tissue of rib-like.As shown in Figure 1A and 1B, the length of placoid scale is generally 100-200 μ m, and the width between rib is 50-100 μ m.The electron scanning micrograph of shark skin surface as shown in Figure 2.Placoid scale is enamel, and quality very hard (microhardness 300-350HV is used as sand paper in ancient times) consists of non-smooth squama sour jujube and buried substrate in corium.Placoid scale and tooth belong to homologous organ (claim again " cosmoid scale "), its form because of shark kind and body part different.This rib structure on placoid scale can be optimized the fluidic structures of shark body surface fluid boundary layer, suppresses and postpone turbulent generation, thereby effectively reduces water body resistance.
Shark skin non-smooth surface structure has superior resistance reducing performance.Pertinent data shows, in the resistance of modern civilian aircraft, surface friction drag almost accounts for 48% of total-resistance; Boats and ships, when motion, are accounted for the 70%-80% of total-resistance by the caused resistance of surface friction; In pipeline transportation, all loss is in surface friction drag for the energy of 80%-100%, and a large amount of energy has been consumed because of the existence of surface resistance.Drag reduction technology all has wide practical use at Military and civil fields, pneumatic covering as complicated in engine blade, fluid delivery tube, aircraft, the pneumatic covering of bullet train, combat unit (battleship, submarine etc.) under water.It is reported, the high precision shark placoid scale structure drag-reduction effect of Polymer materialspreparation is more than 10%, and in visible report, drag-reduction effect reaches as high as 24.6%.
At present, bionical shark skin placoid scale structure replication preparation is mainly divided into two processes: the manufacture of negative sense template and replica are turned over mould.Placoid scale structure is existing preparation method mainly comprise: subfebrile temperature in pression method, micro-plastic casting method, micro-electrocasting and soft lithography etc.
Subfebrile temperature in pression method is hot-forming and combinations vacuum pouring bi-material moulding means, comprise base plate heating, sample stack with exert pressure, demoulding with elasticity, replica turn over mould four steps, first three step is wherein for obtaining having the negative sense template of shark placoid scale structure.In vacuum hotpressing machine, polymethyl methacrylate (PMMA) flat board of take is substrate, and shark skin is tiled on it and is aided with inflatable packer with flat board to be flattened; Under vacuum condition, be warmed up to PMMA second-order transition temperature pressurize for some time, pressurize finishes the negative sense template that the rear demoulding obtains being printed on placoid scale.Replica is turned over mould and is adopted performed polymer vacuum pouring method, PDMS performed polymer and solidifying agent is mixed also degassed in certain mass ratio, is cast in the negative sense template of previous manufacture, is heating and curing, reach predetermined set time after the demoulding just obtain bionical shark skin.
It is basic identical that micro-plastic casting method copies technological process and the micro-embossing method of shark skin, in the negative sense template manufacturing stage, before solidifying in the PDMS performed polymer of certain mass ratio mixing and solidifying agent, clogged shark skin surface and carry out replica, curing and demolding obtains micro-template (negative sense template) that copies.Replica is turned over mode step section, after employing RTV-II silicon rubber replica, makes bionical shark skin.
Micro-electroforming rule is in the negative sense template manufacturing stage, adopts electrocasting to prepare shark skin metallic nickel negative sense template.The metal that electrocasting is conventional is three kinds of copper, nickel, iron, then at negative sense, turns over mode step section, adopts pressure sintering that polythene PE plate is prepared to bionical shark skin in the metallic nickel negative sense template of preparation before.
Vacuum pouring method mainly comprises: in the negative sense template manufacturing stage, to shark skin sample surface pouring liquid duplicating material, then utilize vaccum-pumping equipment to remove the bubble in duplicating material, treat that duplicating material curing and demolding obtains shark skin and copies negative sense template, wherein duplicating material can be fluid silicone rubber, PDMS performed polymer or solidifying agent mixed solution by a certain percentage etc.; Replica is turned over mode step section and is all adopted equally vacuum pouring method.
Micro-nano rolling forming method mainly comprises: in the negative sense template manufacturing stage, adopt magnetron sputtering sputter 0.5 μ m nickel dam on biological shark skin, then adopt spraying technology photoresist material PR1-12000A to be spin-coated on the nickel dam of biological shark skin, at 120 ℃ of baking 180s, then irradiate 365nm length ultraviolet line 6min, through washed with de-ionized water; After photoetching, shark skin is moist and soft, is attached in metallic roll, be placed in loft drier dry after, obtain the roller bearing with shark skin topological framework; Negative sense mould material adopts epoxy resin AW-01, has best plasticity after 45 ℃ of curing 145-150min, completes rapidly rolling process in section between needing at this moment; After roll extrusion completes, completely curing at ambient temperature, thus obtain shark skin negative sense template; In replica, turn over mode step section, adopt injection moulding to prepare the bionical shark skin of silicon rubber in the negative sense template obtaining.
Soft lithography mainly comprises: at elasticity negative sense template preparatory phase, take pretreated shark skin as micro-template that copies, utilize the soft mould technology in soft carving technology to prepare silicon rubber matter elasticity negative sense template; In replica, turn over mode step section, the graft copolymer of aqueous epoxy resins and polyacrylamide of take is base material, and elasticity negative sense template is carried out to replica, and a kind of composite anti-drag shark skin that has nanometer long-chain drag reduction interface and micron groove pattern true to nature concurrently is shaped.
But the material that existing preparation has shark placoid scale structure exists a lot of not enough.One, the scope of application is mainly non-metallic material.At present, in the whole bag of tricks prepared by shark skin placoid scale structure (as subfebrile temperature in pression method, micro-plastic casting method, micro-electrocasting, soft lithography etc.), bionical shark skin is prepared material and be take non-metallic material as main (generally adopting high polymer material, as PDMS performed polymer and curing agent mixture, silicon rubber, polyethylene etc.).Although high polymer material groove can represent goodish drag-reduction effect, can in actual physical situation, due to wearing and tearing, the drag-reduction effect of above-mentioned model can disappear totally very soon; Non-metallic material also can not be applied to high-temperature component in addition, as blade etc.Its two, be difficult in engineering field application.As micro-electrocasting, because the common metal of micro-electrocasting is mainly three kinds of copper, nickel, iron, other metallic substance are as electroforming difficulties such as titanium alloy, aluminium alloy, Al-Li alloys, and can not be used.Micro-nano rolling forming method adopts magnetron sputtering nickel dam, have equally metal_based material restricted problem, and magnetron sputtering efficiency is low.In addition, micro-nano rolling forming method, when negative sense template is prepared in roll extrusion, need to complete operational difficulty in epoxy resin cure specified time.
Therefore, develop a kind of metal matrix component with shark placoid scale structure and preparation method thereof, be still one of this area problem demanding prompt solution.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of metal matrix component with shark placoid scale structure and preparation method thereof.Preparation method of the present invention can realize the preparation of the metallic substance with shark placoid scale structure, can overcome the various shortcomings that adopt non-metallic material.
For reaching above-mentioned purpose, the invention provides a kind of preparation method with the metal matrix component of shark placoid scale structure, it comprises the following steps:
Step 1, preparation shark shield phosphorus biological template;
Step 2, preparation shark placoid scale pottery negative sense template: distilled water, acrylamide (AM) and methylene-bisacrylamide (MBAM, linking agent) are mixed to formation premixed liquid; Aluminum oxide is joined in described premixed liquid, obtain ceramic size; In described ceramic size, add ammonium persulphate (ASP, initiator) and Tetramethyl Ethylene Diamine (TEMED, catalyzer) and mix, then vacuumizing degasification, through 15-30min, obtaining ceramic gelinite; Described ceramic gelinite is injected to described shark shield phosphorus biological template; Then the ceramic gelinite in described shark shield phosphorus biological template is carried out to gradient dehydration, make the dry ceramic blank that forms of described ceramic gelinite; Again by described shark shield phosphorus biological template along the demoulding from dry ceramic blank of placoid scale withdrawing pattern direction, obtain shark shield phosphorus ceramic blank; Described shark shield phosphorus ceramic blank is carried out to sintering, obtain described shark placoid scale pottery negative sense template;
Step 3, preparation have the metal matrix component of shark placoid scale structure: the one side spraying that has shark placoid scale structure in described shark placoid scale pottery negative sense template stops solder flux; The shark placoid scale pottery negative sense template that spraying is stopped after solder flux is placed in jacket; Metal matrix powder is placed in to the spraying of shark placoid scale pottery negative sense template and stops on the face of solder flux, then to thering is the jacket of shark placoid scale pottery negative sense template and metal matrix powder, weld encapsulation; Under oscillating action, make metal matrix powder uniform filling in jacket; Then vacuumize leak detection (if leak, can carry out repair welding); The leak free jacket with shark placoid scale pottery negative sense template and metal matrix powder is carried out to sintering; Then remove jacket, and by metal matrix component demoulding shark placoid scale pottery negative sense template, obtain the described metal matrix component with shark placoid scale structure.
In above-mentioned preparation method, preferably, the aluminum oxide in step 2 is the alumina powder of meso-position radius 0.5-3 μ m.
In above-mentioned preparation method, preferably, the total mass of this ceramic size of take is benchmark, and the solid content of the ceramic size in step 2 is 52-70%.
In above-mentioned preparation method, preferably, the mass ratio of the distilled water in step 2, acrylamide, methylene-bisacrylamide is (69.9-88.5): (11-30): (0.1-0.5).
In above-mentioned preparation method, preferably, the mass ratio of the ceramic size in step 2, ammonium persulphate, Tetramethyl Ethylene Diamine is (90-95.9): (4-9.5): (0.1-0.5).
In above-mentioned preparation method, the ceramic gelinite in described shark shield phosphorus biological template is carried out to the ethanolic soln that gradient dehydration can adopt volume fraction to raise gradually.The method that the ethanolic soln that adopts volume fraction to raise gradually carries out gradient dehydration is the gradient dewatering of this area routine, and its concrete operation step is known to the skilled person.
In above-mentioned preparation method, preferably, the temperature of in step 2, described shark shield phosphorus ceramic blank being carried out to sintering is 1200-1500 ℃, and the time is 20-40min.
In above-mentioned preparation method, preferably, the metal matrix powder in step 3 comprises one or more the combination in the lightweights such as titanium alloy powder, tungsten alloy powder, Al alloy powder and Al-Li alloy powder or high temperature material (alloy).
In above-mentioned preparation method, preferably, the particle diameter≤10 μ m(superfine metal based powders of the metal matrix powder in step 3), more preferably, the particle diameter≤0.8 μ m(nano metal based powders of metal matrix powder).
In above-mentioned preparation method, the only solder flux in step 3 is that high temperature stops solder flux, sprays by quantitatively spraying instrument control system thin film layer thickness≤5 μ m.。In step 3, jacket being welded to encapsulation is to adopt to well known to a person skilled in the art welding method for packing.
In above-mentioned preparation method, preferably, the jacket in step 3 is carbon steel jacket.
In above-mentioned preparation method, preferably, the temperature of in step 3, the leak free jacket with shark placoid scale pottery negative sense template and metal matrix powder being carried out to sintering is 950-1200 ℃, and the time is 8-12h.
In above-mentioned preparation method, preferably, the removal jacket in step 3 adopts mechanical workout or line cutting.
Shark skin placoid scale structure is comprised of spinous process and subcutaneous dermal tissue, and the shark skin directly obtaining need to just can be used for through pre-treatment the preparation of shark placoid scale pottery negative sense template.In above-mentioned preparation method, preferably, the step of preparation shark shield phosphorus biological template comprises: shark skin is organized successively and peeled off, cleans, dewaters, flattens fixing and be dried, obtain described shark shield phosphorus biological template.
In above-mentioned preparation method, preferably, described cleaning adopts aqueous phosphatic as scavenging solution.More preferably, the mass concentration of this aqueous phosphatic is 3-6%.The phosphoric acid salt adopting can be the conventional phosphoric acid salt using in this area.
In above-mentioned preparation method, preferably, described dehydration comprises: the shark shield phosphorus after cleaning is organized at 5 ℃, in glutaraldehyde water solution to fixedly 20-30 hour, then adopts the ethanolic soln that volume fraction raises gradually to carry out gradient dehydration.More preferably, the volumetric concentration of this glutaraldehyde water solution is 25%.The method that the ethanolic soln that adopts volume fraction to raise gradually carries out gradient dehydration is the gradient dewatering of this area routine, and its concrete operation step is known to the skilled person.
In above-mentioned preparation method, preferably, the step of preparation shark shield phosphorus biological template can comprise: shark skin (can be the fresh shark skin of directly buying from seafood market) the trunk epidermis of intercepting certain size, peel off the subcutis of this trunk epidermis, adopt the shark shield phosphorus tissue after aqueous phosphatic clean stripping subcutis; Shark shield phosphorus after cleaning is organized at 5 ℃, in glutaraldehyde water solution to fixedly 20-30 hour, then adopts the ethanolic soln that volume fraction raises gradually to carry out gradient dehydration; With four edges of the shark shield phosphorus tissue after the fixing dehydration of frock, to prevent, in drying process, warpage occurs, then the shark shield phosphorus tissue flattening after fixing is dried, obtain described shark placoid scale biological template.Wherein, those skilled in the art can intercept shark skin trunk epidermis as required, and the size of intercepting can be 50mm * 50mm.The shark shield phosphorus tissue flattening after fixing is dried, can adopts loft drier, dry temperature can be 50-60 ℃, and the time can be 1-2h.
Compared with the prior art, the preparation method with the metal matrix component of shark placoid scale structure of the present invention has following progressive point: one, realized the preparation of the bionical shark skin member of metal matrix; Two, the characteristic based on metallic material components, the placoid scale structure preparing is not easy to wear; Three, metal matrix powdered material can comprise lightweight or the high temperature materials such as titanium alloy, aluminium alloy, Al-Li alloy, superalloy, tungstenalloy, there is future in engineering applications widely, such as the placoid scale drag reduction structural metal matrix component preparing is applied to engine high temperature resistant component etc.; Four, adopt conventional equipment, and existing preparation method mainly adopts specific equipment, as adopted magnetron sputtering equipment to prepare nickel dam in micro-nano rolling forming method on shark skin; The metal matrix component size five, preparing can design according to part feature, is not subject to process technology limit.
The present invention also provides a kind of metal matrix component with shark placoid scale structure, and it is preparation-obtained by the preparation method of the above-mentioned metal matrix component with shark placoid scale structure.
Preparation method of the present invention adopts ceramic gel injection method directly to copy placoid scale structure on shark shield phosphorus biological template, obtain shark placoid scale pottery negative sense template, then metal matrix powder is turned over to mould in shark placoid scale pottery negative sense template and cover type, and then obtain having the metal matrix component of shark placoid scale structure.Preparation method of the present invention expands the placoid scale drag reduction biomimetic features manufacturing process scope of application to metallic substance, makes it have the prospect of engineering application; And solved the easy loss of non-metallic material shark placoid scale structure and lost effect, and can not be applied to the problem of high-temperature component etc.
Accompanying drawing explanation
Figure 1A is the shield phosphorus length schematic diagram of shark skin placoid scale structure.
Figure 1B is the rib spacing schematic diagram of shark skin placoid scale structure.
Fig. 2 is the electron scanning micrograph of shark skin surface.
Fig. 3 is the preparation method's of embodiment 1 schema.
Fig. 4 is preparation method's step 2 and the schematic flow sheet of step 3 of embodiment 1.
Embodiment
For technical characterictic of the present invention, object and beneficial effect being had more clearly, understand, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Embodiment 1
The present embodiment provides a kind of preparation method with the metal matrix component of shark placoid scale structure, and as shown in preparation method's the step 2 of preparation method's schema of Fig. 3 and Fig. 4 and the schematic flow sheet of step 3, it comprises the following steps:
Step 1, preparation shark shield phosphorus biological template: shark skin (can be the fresh shark skin of directly buying from seafood market) the trunk epidermis of intercepting 50mm * 50mm, peel off the subcutis of this trunk epidermis, adopt the shark shield phosphorus tissue after the aqueous phosphatic clean stripping subcutis that mass concentration is 3-6%; By fixing 20-30 hour in the glutaraldehyde water solution that shark shield phosphorus is organized at 5 ℃, volumetric concentration is 25% after cleaning, then adopt the ethanolic soln that volume fraction raises gradually to carry out gradient dehydration; With four edges of the shark shield phosphorus tissue after the fixing dehydration of frock, to prevent, in drying process, warpage occurs, the shark shield phosphorus tissue after then flattening being fixed is placed in loft drier dries 1h at 60 ℃, obtains described shark placoid scale biological template;
Step 2, preparation shark placoid scale pottery negative sense template: distilled water, acrylamide and methylene-bisacrylamide are mixed to formation premixed liquid with the mass ratio of 87.5:12:0.5; The alumina powder that is 0.5-3 μ m by meso-position radius joins in described premixed liquid, obtains the ceramic size that solid content the is 52-70% total mass of this ceramic size (take be benchmark); In described ceramic size, add ammonium persulphate and Tetramethyl Ethylene Diamine and mix, wherein, the mass ratio of ceramic size, ammonium persulphate and Tetramethyl Ethylene Diamine is 94.9:5:0.1, then vacuumizes degasification, through 15min, obtains ceramic gelinite; Described ceramic gelinite is injected to described shark shield phosphorus biological template; Then the ceramic gelinite in described shark shield phosphorus biological template is carried out to gradient dehydration, make the dry ceramic blank that forms of described ceramic gelinite; Again by described shark shield phosphorus biological template along the demoulding from dry ceramic blank of placoid scale withdrawing pattern direction, obtain shark shield phosphorus ceramic blank; Described shark shield phosphorus ceramic blank is carried out to sintering, and the temperature of sintering is 1300 ℃, and the time is 20min, obtains described shark placoid scale pottery negative sense template;
Step 3, preparation have the metal matrix component of shark placoid scale structure: the one side spraying that has shark placoid scale structure in described shark placoid scale pottery negative sense template stops solder flux; Then the only face of solder flux that do not spray of take is the contact surface with carbon steel jacket, and the shark placoid scale pottery negative sense template that spraying is stopped after solder flux is placed in carbon steel jacket; Metal matrix powder is placed in to the spraying of shark placoid scale pottery negative sense template and stops on the face of solder flux, then to thering is the carbon steel jacket of shark placoid scale pottery negative sense template and metal matrix powder, weld encapsulation; On shaking platform, make metal matrix powder uniform filling in carbon steel jacket; Then with vacuum pump, vacuumize leak detection; The leak free carbon steel jacket with shark placoid scale pottery negative sense template and metal matrix powder is carried out to sintering, and the temperature of sintering is 1000 ℃, and the time is 10h; Then adopt mechanical workout or line cutting to remove carbon steel jacket, and the metal matrix component that sintering is obtained demoulding shark placoid scale pottery negative sense template, the described metal matrix component with shark placoid scale structure obtained; Wherein, described metal matrix powder comprises one or more the combination in the lightweights such as titanium alloy powder, tungsten alloy powder, Al alloy powder and Al-Li alloy powder or high temperature material (alloy).
Claims (10)
1. a preparation method with the metal matrix component of shark placoid scale structure, it comprises the following steps:
Step 1, preparation shark shield phosphorus biological template;
Step 2, preparation shark placoid scale pottery negative sense template: distilled water, acrylamide and methylene-bisacrylamide are mixed to formation premixed liquid; Aluminum oxide is joined in described premixed liquid, obtain ceramic size; In described ceramic size, add ammonium persulphate and Tetramethyl Ethylene Diamine and mix, then vacuumizing degasification, through 15-30min, obtaining ceramic gelinite; Described ceramic gelinite is injected on described shark shield phosphorus biological template; Then the ceramic gelinite in described shark shield phosphorus biological template is carried out to gradient dehydration, make the dry ceramic blank that forms of described ceramic gelinite; Again by described shark shield phosphorus biological template along the demoulding from dry ceramic blank of placoid scale withdrawing pattern direction, obtain shark shield phosphorus ceramic blank; Described shark shield phosphorus ceramic blank is carried out to sintering, obtain described shark placoid scale pottery negative sense template;
Step 3, preparation have the metal matrix component of shark placoid scale structure: the one side spraying that has shark placoid scale structure in described shark placoid scale pottery negative sense template stops solder flux; The shark placoid scale pottery negative sense template that spraying is stopped after solder flux is placed in jacket; Metal matrix powder is placed in to the spraying of shark placoid scale pottery negative sense template and stops on the face of solder flux, then to thering is the jacket of shark placoid scale pottery negative sense template and metal matrix powder, weld encapsulation; Under oscillating action, make metal matrix powder uniform filling in jacket; Then vacuumize leak detection; The leak free jacket with shark placoid scale pottery negative sense template and metal matrix powder is carried out to sintering; Then remove jacket, and by metal matrix component demoulding shark placoid scale pottery negative sense template, obtain the described metal matrix component with shark placoid scale structure.
2. preparation method according to claim 1, wherein, the aluminum oxide in step 2 is the alumina powder of meso-position radius 0.5-3 μ m.
3. preparation method according to claim 1, wherein, the total mass of the ceramic size in step 2 of take is benchmark, the solid content of this ceramic size is 52-70%.
4. preparation method according to claim 1, wherein, the mass ratio of the distilled water in step 2, acrylamide, methylene-bisacrylamide is (69.9-88.5): (11-30): (0.1-0.5).
5. preparation method according to claim 1, wherein, the mass ratio of the ceramic size in step 2, ammonium persulphate, Tetramethyl Ethylene Diamine is (90-95.9): (4-9.5): (0.1-0.5).
6. preparation method according to claim 1, wherein, the metal matrix powder in step 3 comprises one or more the combination in titanium alloy powder, tungsten alloy powder, Al alloy powder and Al-Li alloy powder.
7. preparation method according to claim 1, wherein, the removal jacket in step 3 adopts mechanical workout or line cutting.
8. preparation method according to claim 1, wherein, the step of preparation shark shield phosphorus biological template comprises: shark skin organize successively and peeled off, cleans, dewaters, flattens fixing and be dried, the shark shield phosphorus biological template described in obtaining.
9. preparation method according to claim 8, wherein, described cleaning adopts aqueous phosphatic as scavenging solution; Described dehydration comprises: the shark shield phosphorus after cleaning is organized at 5 ℃, in glutaraldehyde water solution to fixedly 20-30 hour, then adopts the ethanolic soln that volume fraction raises gradually to carry out gradient dehydration.
10. a metal matrix component with shark placoid scale structure, it is preparation-obtained by the preparation method of the metal matrix component with shark placoid scale structure described in claim 1-9 any one.
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