CN106467939A - A kind of multi-stage porous metal fabrication methods - Google Patents
A kind of multi-stage porous metal fabrication methods Download PDFInfo
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Abstract
The invention discloses a kind of multi-stage porous metal fabrication methods, specially：The preparation aperture porous metal film same or equivalent with waiting the minimum one-level hole aperture making multistage mesoporous metal, then being broken for dimensional maximums is the granule waiting to make multistage mesoporous metal minimum one-level hole aperture average 6-40 times, granule is made slurry, is uniformly impregnated with having than on the high-molecular organic material support waiting to make the big upper level hole in multistage mesoporous metal minimum one-level hole；Vacuum or protective atmosphere sinter, carries out conventional subsequent treatment according still further to metal material technique, that is, multistage mesoporous metal is obtained.This kind of method can efficiently control pore size, the arrangement in hole, connectivity, the material connectivity of preparation is good, holes at different levels are all each mutually communicated and hole at different levels also insertion each other each other, can be used as the multiple materials such as biomaterial, filtering material, can meet several functions demand, preparation method is simple, be easily achieved.
Description
Technical field
The present invention relates to porous metals are and in particular to a kind of preparation method of multistage mesoporous metal.
Background technology
Porous metals are a kind of new engineering material having function and structure double attribute concurrently, this material not only remains the metallic characters such as solderability, electric conductivity and ductility, and possessing the characteristics such as bulk density is low, specific surface area big, energy-absorbing damping, sound-deadening and noise-reducing, electromagnetic shielding, air-and water-permeable, lower thermal conductivity, it is applied and is being continuously increased.The traditional method preparing porous metals at present mainly has powder metallurgic method, fiber sintering method, foam melt method, melt air blast, infiltration casting, metaliding, hollow ball sintering process, self-propagating high-temperature synthesis, foam impregnation method etc.；Taking foam impregnation method as a example, patent CN
Method disclosed in a kind of preparation method of medical metal implantation material porous tantalum of 102462861 A is：The solution being configured to organic binder bond and dispersant, make tantalum powder slurry with the mixed powder of starch and ta powder, and be cast in Organic Foam Material, dipping is until Organic Foam Material hole fills tantalum powder slurry, then it is dried and remove the dispersant being cast with the Organic Foam Material of tantalum powder slurry, under inert gas shielding atmosphere, ungrease treatment is to remove organic binder bond and Organic Foam Material, sinter under vacuum and porous sintered body is obtained, sintered pure tantalum powder is piled up on the foam framework constituting, tantalum powder granule has sintering neck structure each other, under vacuum, annealing and conventional post processing are obtained porous tantalum again.The major defect of these methods above-mentioned is that the material pore structure prepared is single, and it is difficult to control to pore size and connectedness etc., pore structure single such that it does not meeting several functions demand, pore size and connectedness be difficult to control to by make material can not fully, be accurately finished required function.
In recent years, there is the preparation of the material of hierarchical porous structure and application has become as a very active research frontier in the world, and become following study hotspot.Either in biotechnology, biological medicine, catalysis, the energy, optics, the application of aspect such as separate, or biological solid carrier technology is in the application of photosynthesis and cell therapy, multilevel hole material is of interest by substantial amounts of field.At present, mostly in nanometer range, several nanometers to several tens of nanometers, aperture is little in the multilevel hole material one side aperture studied, and a lot of applications are more much bigger than this value；On the other hand, the multilevel hole material studied is most to be nonmetallic materials, is related to the predominantly metal oxide materials of metal, metal and alloy little, and much apply the multilevel hole material needing metal and alloy.Despite researcher be made that the multilevel hole material relevant with metal, such as CN201410337365 macroscopic view-microcosmic-nanometer hierarchy mechanics suitability bone repair and its preparation, describe a kind of bone repair.It includes macroporosity metal structure, micropore structure body and nanofiber, and the size of internal macroporosity is 300-1500
Micron, mutually connects between each macroporosity completely, and micropore structure body is located within the metal structure of macroporosity, and internal micropore structure connects hole between mutually uniformly and completely, and pore-size is 50-250
Micron；The pore wall of microscopic void is made up of nanofiber, but it is the nonmetallic and nanofiber composition of a kind of porous metals of hole and another kind of hole, and its preparation method is unable to the size in effective control hole.The preparation of metal multilevel hole material is more difficult due to technical reason, and research is seldom.
Content of the invention：
It is an object of the invention to provide a kind of effectively controlled porous metals preparation method with hierarchical porous structure.
If it has been recognised by the inventors that first preparing the metal material with next stage hole, then constructing upper level pore structure with it as cavity wall, you can prepare the metal material with two-stage hole, the like, the metal material in the above hole of two-stage can be prepared.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of porous metals, comprises the steps：
（1）Material prepares
Prepare aperture and wait to make the same or equivalent porous metal film in multistage mesoporous metal minimum one-level hole aperture, being then broken for dimensional maximums is the granule waiting to make multistage mesoporous metal minimum one-level hole aperture average 6-40 times；
（2）Above-mentioned granule is made slurry, is uniformly impregnated with having on the high-molecular organic material support in upper level hole bigger than the minimum one-level hole of multistage mesoporous metal to be made；
（3）High-molecular organic material support is sintered in vacuum or protective atmosphere, carries out conventional subsequent treatment according still further to the metal material technique waiting the raw material making multistage mesoporous metal, the multistage mesoporous metal with two-stage hole is obtained.
Above-mentioned granule, because being that porous metal film pulverizes formation, is non-regular shape, describes its particle size upper limit with dimensional maximums.
After sintering, high-molecular organic material support volatilizees, and forms two-stage hole.
Further, before dipping, first by（1）The granule that step is obtained uniformly is mixed with the pore creating material in the hole waiting the big one-level in the minimum one-level hole making multistage mesoporous metal for preparation ratio, make slurry, on the high-molecular organic material support being uniformly impregnated with again have the hole in big two grades of the minimum one-level hole than multistage mesoporous metal to be made, so, so that it may prepare the multi-stage porous metal material with three-level hole after sintered.The like, also can prepare the porous metal material in more stages hole.
More specifically, the preparation method of described multistage mesoporous metal, the hole of macromolecular material support is three-dimensional insertion, thus the hole prepared is also three-dimensional insertion.
More specifically, described porous metal film is prepared with template, the organic film that template can be processed for aluminum oxide film, bubble hydrogen template or track etch method, and above-mentioned template can easily prepare required porous metal film.
More specifically, the preparation method of described porous metal film is：Using dip coating, metal powder pulp is coated on rustless steel, carries out vacuum-sintering, remove rustless steel, that is, required porous metal film is obtained.The method process is simple, low cost, uniform texture.
More specifically, described porous metals preparation method, metal can be one of tantalum, niobium, titanium, titanium alloy, rustless steel, cobalt-base alloyss, nickel, nickel alloy, copper, copper alloy or arbitrarily multiple.
More specifically, described porous metals preparation method, pore creating material can be one or more of carbamide, ammonium sulfate, ammonium chloride, methylcellulose, sodium bicarbonate, ethyl cellulose, ammonium hydrogen carbonate, sodium carbonate, starch or flour.
Beneficial effects of the present invention：
（1）The invention provides a kind of method of more than two grades multistage mesoporous metals of effective preparation, by preparing aperture and waiting to make the same or equivalent porous metal film in multistage mesoporous metal minimum one-level hole aperture, then being broken for dimensional maximums is the granule waiting to make multistage mesoporous metal minimum one-level hole aperture average 6-40 times, these granules have minimum one-level hole, above-mentioned granule is made slurry, it is uniformly impregnated with having on the high-molecular organic material support in upper level hole bigger than the minimum one-level hole of multistage mesoporous metal to be made, high-molecular organic material support is sintered in vacuum or protective atmosphere, after sintering, high-molecular organic material support volatilizees, form upper level hole.If before dipping, first will crush the granule being obtained and be used for preparing the hole that ratio waits the big one-level in the minimum one-level hole making multistage mesoporous metal（Second level hole）Pore creating material uniformly mix, make slurry, then be uniformly impregnated with the hole having than big two grades of minimum one-level hole waiting to make multistage mesoporous metal（First order hole）High-molecular organic material support on, after then sintering, high-molecular organic material, pore creating material volatilization, form respectively ratio and wait to make big two grades of the minimum one-level hole of multistage mesoporous metal, the hole of big one-level, define three-level pore structure, namely high-molecular organic material support volatilization formed the cavity wall in maximum one-level hole on have pore creating material formed second level hole, the cavity wall in second level hole has porous metal film formation the third level（Minimum one-level）Hole, holes at different levels classification in order, makes the arrangement in pore sizes at different levels, hole be effectively controlled by controlling material, process sequence, parameter.
（2）The preparation method of the multistage mesoporous metal that the present invention provides, is capable of the three-dimensional insertion in hole, including every grade of hole three-dimensional insertion, holes at different levels three-dimensional insertion mutually.The preparation method of porous metal film ensure that interpenetrating of minimum one-level hole, the macromolecular material support of three-dimensional insertion ensure that interpenetrating of its big one-level hole being formed, granule after broken is in the cavity wall in the big one-level hole that high-molecular organic material support is formed, so that being interpenetrated with the big one-level hole that high-molecular organic material support is formed in minimum one-level hole；When using pore creating material, because the broken granule being obtained equably is mixed with the pore creating material in the hole waiting the big one-level in the minimum one-level hole making multistage mesoporous metal for preparation ratio, after making slurry, it is uniformly impregnated with having on the high-molecular organic material support than the hole waiting the big two grades of sizes in the minimum one-level hole making multistage mesoporous metal again, in addition make material volatilization used by slurry, so that interpenetrating in the second level hole that pore creating material is formed, between minimum one-level hole and second level hole, the macropore that second level hole is formed with high-molecular organic material support（First order hole）Between also interpenetrate.
（3）The preparation method of porous metal film can guarantee that the uniformity in minimum one-level hole, by controlling uniformity and the sintering parameter of high-molecular organic material bracket holes, can guarantee that the uniformity in big one-level hole, by controlling pore creating material property uniform in size and so that pore creating material is uniformly mixed with crushed particles, can guarantee that the uniformity in intergrade hole.
（4）The preparation method of the multistage mesoporous metal that the present invention provides, easy, be easily achieved, parameter is easy to adjust control, and porous metal film is easily prepared, and pulverize convenient.
Brief description
Below in conjunction with accompanying drawing, the present invention is further elaborated with embodiment.
Fig. 1 is preparation method flow chart of the present invention；
The multistage mesoporous metal schematic diagram that Fig. 2 is prepared for the present invention.
Specific embodiment
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is explained, embodiment, premised on technical solution of the present invention, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited only to embodiment disclosed below.
As shown in figure 1, it gives multistage mesoporous metal preparation flow：First carry out material preparation, prepare aperture and wait that the minimum one-level hole aperture size making multistage mesoporous metal is same or equivalent, the more precisely substantially suitable porous metal film of aperture size, then being broken for dimensional maximums is the granule waiting to make multistage mesoporous metal minimum one-level hole aperture average 6-40 times, granule is made slurry, on the high-molecular organic material support being uniformly impregnated with have the upper level hole bigger than waiting the minimum one-level hole making multistage mesoporous metal, vacuum or protective atmosphere sinter, carry out conventional subsequent treatment according still further to metal material technique, multistage mesoporous metal is obtained.
As shown in Figure 2, the figure illustrates multi-stage porous metal structure, this multistage mesoporous metal has second hole structure, and 1 is macropore, and 2 is the cavity wall of macropore, 3 is the aperture in macropore cavity wall 2, macropore 1 passes through passage 4 and other macropore insertions, similarly, aperture 3 also in this way with other aperture insertions, as seen from the figure, macropore 1 and aperture 3 are also be mutually communicated.
Embodiments of the invention are given in detail below：
Embodiment
1
：
The present embodiment is to prepare the porous niobium with second hole, and its preparation method is：
（1）Material prepares
First prepare organic film with track etch method：Make the High energy particles Radiation that thickness is that 5 μm of -15 μm of polycarbonate films accept perpendicular to thin film, in the presence of radiating particle, track is formed on thin film, then thin film is immersed in sulfuric acid solution and process 3 hours, the thin-film material at track is made to be corroded and obtain having very narrow pore-size distribution, uniform cylindrical hole, aperture is 200 nm -600nm.
With JGP560 ultra-high vacuum multifunctional sputter on thin film r. f. magnetron sputtering metal niobium pentoxide film, remove polycarbonate film, prepared porous metals niobium pentoxide film, be then broken for the granule that full-size is 6 m -8 m；
（2）By polyvinyl alcohol and distilled water according to 1：19 part by weight mixing, heating, polyvinyl alcohol dissolves, by the mixed solution of above-mentioned granule and polyvinyl alcohol and distilled water according to part by weight 1：5 make slurry, are uniformly impregnated with the polyurethane foam that aperture is 70 m -150 m；
（3）Polyurethane foam after dipping is sintered in vacuum or protective atmosphere, carries out conventional subsequent treatment according still further to niobium technique, the porous niobium with two-stage hole is obtained, the macropore that it is mutually communicated is 60 m
- 130 m, the cavity wall of macropore has the aperture of the 170nm-550nm interpenetrating, the also insertion each other each other of two-stage hole, and overall porosity is 77%.
Above-mentioned broken particle size maximum is 16-22 times of minimum one-level hole aperture average.
This kind of porous niobium material can be used as bone implant.
Embodiment
2
：
The present embodiment is the porous cobalt prepared and have second hole, and its preparation method is：
（1）Material prepares
First prepare aluminum oxide film：High-purity aluminium flake (99.99%) is placed in the lower 650 DEG C of annealing 1h of hydrogen environment, eliminates the residual stress in aluminium flake；It is cleaned by ultrasonic 10 with acetone, dehydrated alcohol respectively
Min, goes to degrease；In the mixed solution of 25 DEG C of perchloric acid and dehydrated alcohol, (volume ratio is 1：4) use 21V voltage to polish 5min in, obtain bright even curface.With graphite as negative electrode, the aluminium flake after polishing is anode, carries out two-step anodic oxidization in 0-5 DEG C of 0.3 mol/L oxalic acid for electrolyte, and oxidation voltage is 40 V；First step anodizing time is 12h, is completely dissolved alumina layer at room temperature with the mixed liquor of chromic acid and phosphoric acid after oxidation；Ask as 24 h during second step anodic oxidation, use saturation copper chloride solution to pass through displacement reaction after terminating and remove not oxidized metallic aluminium.Finally, remove potential barrier layer with 5% phosphoric acid and form doubled via, and reaming 25
Min is obtained required porous anodic alumina film, and aperture is 80nm-100nm.
Plate last layer cobalt film using ion sputtering film coating machine on anodic aluminum oxide film surface, be completely dissolved alumina layer at room temperature with the mixed liquor of chromic acid and phosphoric acid, prepared cobalt film, aperture is 80nm-100nm, is then broken for the granule that full-size is 2 m -3 m；
（2）By polyvinyl alcohol and distilled water according to 1：19 part by weight mixing, heating, polyvinyl alcohol dissolves, by the mixed solution of above-mentioned granule and polyvinyl alcohol and distilled water according to part by weight 1：5 make slurry, are uniformly impregnated with the polyurethane foam that aperture is 230 m -380 m；
（3）Polyurethane foam after dipping is sintered in vacuum or protective atmosphere, carries out conventional subsequent treatment according still further to cobalt technique, the porous cobalt with two-stage hole is obtained, the macropore that it is mutually communicated is 200 m
- 350 m, the cavity wall of macropore has the aperture of the 70nm-90nm interpenetrating, the also insertion each other each other of two-stage hole, and overall porosity is 80%.
Above-mentioned broken particle size maximum is 25-37 times of minimum one-level hole aperture average.
This kind of porous cobalt material can be used as bone implant.
Embodiment
3
：
The present embodiment is to prepare the nickel porous with second hole, and its preparation method is：
（1）Material prepares
Prepare nickel thin film with bubble hydrogen template：Take cathode substrate material be nickel sheet (
99.99%), nickel sheet being positioned in detergent water is cleaned by ultrasonic after oil removing, and in etching solution, standing treats that surface is paved with bubble and takes out, and deionized water rinsing is put into and soaked l0s taking-up in polishing fluid, deionized water is rinsed well, dries.At 20 DEG C, 3A cm-2Electric current density under electroplate, NiCl concentration be 0.1 M, NH4Cl concentration 2M, the bubble hydrogen on coating makes coating become nickel porous thin film.
The nickel sheet of deposited porous nickel coating is sequentially placed into 0.
Embathe in the formaldehyde of 2wt%, deionized water, ethanol, acetone soln, and be dried in a nitrogen atmosphere.Porous nickel coating aperture is 5 m, processes porous nickel coating with milling method, and then milling bits is pulverized the granule for 30 m -40 m.
（2）By polyvinyl alcohol and distilled water according to 1：19 part by weight mixing, heating, polyvinyl alcohol dissolves, by the mixed solution of above-mentioned granule and polyvinyl alcohol and distilled water according to part by weight 1：5 make slurry is uniformly impregnated with the polyester form that aperture is 400 m -550 m again；
（3）Polyester form after dipping is sintered in vacuum or protective atmosphere, carries out conventional subsequent treatment according still further to nickel technique, the nickel porous with two-stage hole are obtained, the macropore that it is mutually communicated is 360 m
- 500 m, the cavity wall of macropore has the aperture of 5 m interpenetrating, the also insertion each other each other of two-stage hole, and overall porosity is 76%.
Above-mentioned broken particle size maximum is 6-8 times of minimum one-level hole aperture average.
This kind of porous nickel materials can be used as filtering material.
Embodiment
4
：
The present embodiment is to prepare the porous tantalum with three-level hole, and its preparation method is：
（1）Material prepares
With the pure tantalum of 400 mesh (99%) as raw material, by tantalum powder and zinc stearate by volume 1：4 be sufficiently mixed after add appropriate dehydrated alcohol, be slowly added to a small amount of dimethyl methyl phthalein amine with vigorous stirring, form evengranular slurry, thickness is 0. 3
The stainless steel substrates deionized water of mm be cleaned by ultrasonic twice after natural air drying, it is then immersed in 100s in tantalum powder slurry, lift out with the speed of 0.5mm/s, wet film puts into sintering 2h in vacuum drying oven after spontaneously drying in atmosphere, take out sample when in-furnace temperature naturally cools to room temperature, after porous tantalum film is separated with stainless steel base, it is placed again in vacuum drying oven, take out after sintering 30min again, the aperture of porous tantalum film is 90nm-260nm, thickness is 70 m, is then broken for the granule that particle diameter is 3 m -6 m；
（2）Take the starch that particle diameter is 90nm-260nm, according to part by weight 1：40 are mixed with distilled water, make starch solution, by above-mentioned granule, particle diameter be 30 m-60 m methylcellulose and starch solution according to part by weight 13：1：8 make slurry, are uniformly impregnated with the polyester form that aperture is 300 m -500 m；
（3）Polyester form after dipping is sintered in a vacuum furnace, carries out conventional subsequent treatment according still further to tantalum technique, the porous tantalum with three-level hole is obtained, the macropore that it is mutually communicated is 260 m
- 450 m, the cavity wall of macropore have the second hole of the 25 m-50 m interpenetrating, the cavity wall of second hole have the three-level hole of the 70nm-230nm interpenetrating, holes at different levels also insertion each other each other, and overall porosity is 85%.
Above-mentioned broken particle size maximum is 20-40 times of minimum one-level hole aperture average.
This kind of porous tantalum can be used as bone-regeneration material, and first order hole size is used for meeting the demand that the vital tissues such as blood vessel are grown into；Second level hole is used for living away from home of various kinds of cell；Third level hole be particularly conducive to meet cell stick, differentiation demand, the quick response of energy active cell, and because specific surface area is big, a lot of somatomedin can be loaded, and, the connectivity in hole is good, holes at different levels are all each mutually communicated and hole at different levels also insertion each other each other, infiltration, the transmission of tissue fluid can fully be met, realize protein degradation products and the discharge of metabolism product, therefore it is a kind of real bone-regeneration material.
The above, be only presently preferred embodiments of the present invention, and not the structure of the present invention is made with any pro forma restriction.Any simple modification, equivalent variations and modification that every technical spirit according to the present invention is made to above example, all still fall within the range of technical scheme.
Claims (9)
1. a kind of multi-stage porous metal fabrication methods, its feature comprises the steps：
（1）Material prepares
The preparation aperture porous metal film same or equivalent with waiting the minimum one-level hole aperture making multistage mesoporous metal, being then broken for dimensional maximums is the granule waiting to make multistage mesoporous metal minimum one-level hole aperture average 6-40 times；
（2）Above-mentioned granule is made slurry, on the high-molecular organic material support being uniformly impregnated with have the higher level hole bigger than waiting the minimum one-level hole making multistage mesoporous metal；
（3）High-molecular organic material support is sintered in vacuum or protective atmosphere, carries out conventional subsequent treatment according still further to metal material technique.
2. multi-stage porous metal fabrication methods as claimed in claim 1 it is characterised in that：Before dipping, first described granule is uniformly mixed than the pore creating material in the hole waiting the big one-level in the minimum one-level hole making multistage mesoporous metal with being used for preparing, make slurry, then be uniformly impregnated with having on the high-molecular organic material support than the hole in big two grades of minimum one-level hole waiting to make multistage mesoporous metal.
3. multi-stage porous metal fabrication methods as claimed in claim 1 or 2 it is characterised in that：The hole of described macromolecular material support is three-dimensional insertion.
4. multi-stage porous metal fabrication methods as claimed in claim 1 or 2 it is characterised in that：Described porous metal film is prepared with template, and template is the organic film that aluminum oxide film, bubble hydrogen template or track etch method are processed.
5. multi-stage porous metal fabrication methods as claimed in claim 3 it is characterised in that：Described porous metal film is prepared with template, and template is the organic film that aluminum oxide film, bubble hydrogen template or track etch method are processed.
6. multi-stage porous metal fabrication methods as claimed in claim 1 or 2 it is characterised in that：The preparation method of described porous metal film is：Using dip coating, metal powder pulp is coated on rustless steel, carries out vacuum-sintering, remove rustless steel, that is, required porous metal film is obtained.
7. multi-stage porous metal fabrication methods as claimed in claim 3 it is characterised in that：The preparation method of described porous metal film is：Using dip coating, metal powder pulp is coated on rustless steel, carries out vacuum-sintering, remove rustless steel, that is, required porous metal film is obtained.
8. the multi-stage porous metal fabrication methods as described in claim 1-7 any claim item it is characterised in that：Described metal can be one of tantalum, niobium, titanium, titanium alloy, rustless steel, cobalt-base alloyss, nickel, nickel alloy, copper, copper alloy or arbitrarily multiple.
9. the multi-stage porous metal fabrication methods as described in claim 2-8 any claim item it is characterised in that：Described pore creating material can be one or more of carbamide, ammonium sulfate, ammonium chloride, methylcellulose, sodium bicarbonate, ethyl cellulose, ammonium hydrogen carbonate, sodium carbonate, starch or flour.
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