TWI636159B - Porous materials and? systems and methods of fabricating thereof - Google Patents

Abstract

A porous material comprising a specific surface area greater than 10/mm, and a method and system for making the porous material. The porous material includes a plurality of pores having a size that is substantially uniform and varies by less than about 20%, wherein the size is greater than about 100 nanometers and less than about 5 millimeters. A system comprising the porous material can be designed as one of a desalination system, an ultra-micro bubble generating system, a capacitor system, or a battery system.

Description

Porous material and system and method of manufacturing same

The present invention relates to a material and system and a method of manufacturing the same, and more particularly to a porous material and system and method of making the same.

A porous material such as a metal foam may have a high surface area to volume ratio, for example, ,among them, For specific surface area, d is the average pore diameter in millimeters and θ is the porosity. For example, for d = 0.01 mm, 90% porosity, the specific surface area is 2425 / mm. Porous materials can exhibit mechanical, acoustic, thermal, optical, electrical, and chemical properties for a variety of applications.

The present invention is directed to a manufacturing system and method for making large-sized porous materials having a high surface area to volume ratio.

Conventional metal foams can have a hole size of 0.5 to 8 mm. It is possible to produce a porous block having a specific surface area of 14 to 3100 / mm. However, these hole sizes have a large amount of variation, for example greater than 100%.

Some embodiments disclosed herein can produce a surface-area-to-volume ratio porous film having a surface area greater than 100 square centimeters (such as 20 centimeters by 20 centimeters). The dimensions of the holes may be, for example, about 100 nm to 5 mm.

A manufacturing system capable of producing large-sized, high-surface-area porous materials is disclosed herein. The system can include: a colloidal particle template forming portion designed to produce a colloidal particle template; a permeate portion designed to infiltrate a permeate material into the colloidal particle template; and a template removal portion designed to The osmotic material removes the colloidal particle template to obtain the macroporous material.

In some embodiments, the particle template forming portion includes an assembly device designed to self-assemble the charged particles into an array. The assembly device may include an electrophoresis tank, a DC power supply, a pump system having a colloidal suspension, a reference electrode, and a working electrode, wherein an electrophoresis solution including suspended charged template particles is disposed on the electrophoresis The reference electrode and the working electrode may be vertically or horizontally disposed in the electrophoresis tank; and the working electrode provides a surface for electrophoretically manufacturing the particle template. In some embodiments, the template particles are colloidal particles and the resulting particle template is a colloidal particle template.

In some embodiments, a baked portion is further provided after the colloidal particle template forming portion to dry the colloidal particle template produced by the colloidal particle template forming portion, thereby increasing the mechanical strength of the colloidal particle template.

In some embodiments, an asymmetric electric field can be used to make a large size porous material. In some embodiments, the reference electrode and the working electrode of the assembly device are configured such that an asymmetric electric field is formed between the reference electrode and the working electrode. In addition, the asymmetric electric field can also be achieved by setting the size of the reference electrode to be larger or smaller than the size of the working electrode.

In some embodiments, the reference electrode of the assembly device can be rectangular or cylindrical. The working electrode of the assembly device may be a rigid planar conductor made of a metal plate, a germanium wafer, or an indium tin oxide (ITO) glass plate. In some embodiments, the working electrode can be a flexible and movable conductive tape, or a conductive carbon film or carbon tube, such as for a roll by roll process. The conductive tape may be, for example, an ITO tape, a flexible glass having an ITO film, or the like. a leak-proof inlet can be formed on one side wall of the electrophoresis tank such that the flexible and movable conductive tape can enter the electrophoresis tank to provide a surface of the colloidal particle template by an assembly process Thus, the surface charged particles can be deposited on the surface to form an array. The use of the flexible and movable conductive tape as the working electrode allows for a higher degree of automation of the system, and the porous materials can be manufactured by a tape and loop process.

In some other embodiments, the working electrode is not required. For example, a sol-gel method, a chemical vapor deposition method (CVD), or a physical vapor deposition method (PVD), which does not require the conductive tape or substrate, can be used to cut (slice) By slice) to manufacture.

In some embodiments, the permeable portion can be a physical vapor deposition device, a chemical vapor deposition (CVD) device, a sol gel device, or an electroless plating device. In addition, the permeable portion may be an electrophoretic deposition (EPD) device, which may include an EPD tank, a DC power supply, a reference electrode, and a working electrode, wherein an EPD solution may be disposed in the EPD tank. And the working electrode can be designed to carry the colloidal particle template and also provide as a surface on the colloidal particle template for electrophoretic deposition of the permeate in the EPD cell. The DC power source has a voltage in the range of about 0.01 volts to 500 volts and an electric field in the range of about 0.1 to 1000 volts per centimeter. The voltage or electric field strength can be selected based on the size of the colloidal particles.

In some embodiments, the working electrode of the EPD device can be a rigid flat conductor or a flexible and movable conductive strip. In the latter case, a leak-proof inlet and a leak-proof outlet can be disposed on the side wall of the EPD groove, so that the flexible and movable conductive tape can be separately leak-free and Leave the EPD slot.

In some embodiments, the template removal portion can be a toasting device that removes the colloidal particle template from the permeate by heating. In some other embodiments, the template removal portion can be a chemical etching device that can include an etch bath having an etching solution disposed therein. The colloidal particle template can be removed by the etching solution while retaining only the permeating substance. In addition, when a flexible and movable conductive tape is used in the system, the chemical etching device may have a leak-proof inlet disposed on the sidewall of the etching groove and a leak-proof outlet for transporting the colloid The particle template and the flexible and movable conductive web of the permeable material can enter and exit the etch bath without leakage, respectively.

In some embodiments, the system can further include a device designed to separate the osmotic material from the flexible and movable conductive tape to obtain the porous material and recover the flexible and movable Conductive tape. For example, a splitting knife may be disposed between the conductive web and the porous material, and the web and the porous material may be separated such that the porous material forms a roll film at a first reel while utilizing a The second reel is used to recover the conductive tape.

A method of making a porous material using the foregoing system is also disclosed herein. The method can include the step (1) of using the colloidal particle template forming portion to prepare substantially uniform (e.g., single size) colloidal particles (e.g., in terms of standard deviation, the dimensional change is less than ± 20%, such as ± 10%) manufacturing a colloidal particle template; step (2), using the permeating portion, infiltrating a permeate material into the colloidal particle template; and step 3), removing the template using the template removal portion, and finally obtaining the complete The permeating substance acts as the porous material. In some cases, the template is referred to as a crystal template because the template particles (e.g., colloidal particles) are densely packed into a crystal-like structure.

In some embodiments, the method may further include, after the step (1) and before the step (2), using a baking portion to immediately dry the colloidal particle template to increase the mechanical structure of the colloidal particle template. strength. For example, the baking temperature can be from 90 to 500 ° C and can be adjusted based on the materials used. The relative humidity can be greater than 75 and the baking time can be from about 0.5 to 2 hours. The range of baking temperatures is chosen based on the materials used. For example, for polystyrene, the annealing temperature can be from about 90 to 100 ° C and the baking time can be about 30 minutes. For cerium oxide, the annealing temperature can be about 450-500 ° C and the baking time can be about 1.5 hours.

In some embodiments, step (1) of the method may involve using the assembly device as described above as the colloidal particle template forming portion, wherein an electrophoresis solution including suspended particles may be placed in the electrophoresis tank; a reference electrode and the working electrode may be vertically disposed in the electrophoresis tank; the reference electrode is cylindrical; the working electrode provides a surface for electrophoretically manufacturing the colloidal particle template; and the reference electrode and the working electrode An electric field between them is set in the range of about 0.05 V/cm - 1000 V/cm.

In some embodiments, the assembly device in step (1) of the method may use an ethanol solution comprising suspended colloidal particles such as polystyrene, ceria, and polymethyl methacrylate (PMMA). The corresponding colloidal particle template is electrophoretically produced. The particle size can range from about 100 nm to 5 mm. The pH of the ethanol solution can be in the range of about 4-9 and can be adjusted by the addition of aqueous ammonia or nitric acid. In some other embodiments, an organic solvent, water, or a water mixed solvent may be used in place of the ethanol.

In some embodiments, the working electrode of the assembly device can be a solid plate conductor selected from a metal plate, a germanium wafer, or an indium tin oxide (ITO) glass plate.

In some embodiments, the working electrode of the assembly device can be a flexible and movable conductive tape that can be stationary or moved at a speed between 100 nm/sec and 10 cm/sec. . A leak-proof inlet can be disposed on one side wall of the electrophoresis tank such that the flexible and movable conductive tape can enter the electrophoresis tank.

In some embodiments, a physical vapor deposition apparatus, a chemical vapor deposition apparatus, a sol-gel apparatus, or an electroless plating apparatus may be used as the permeation part in the step (2) to The osmotic material penetrates into the colloidal particle template produced in the step (1).

In some embodiments, the permeation in step (2) can be achieved using an electrophoretic deposition (EPD) apparatus as described above, wherein: the EPD solution comprising a permeable substance can be disposed in the EPD tank; transporting the colloidal particle template The working electrode can be designed to provide a surface for electrophoretical deposition of the osmotic material onto the colloidal particle template within the EPD cell.

In some embodiments, the working electrode of the EPD device used in step (2) can be a rigid flat conductor, or a flexible and movable conductive tape. In the latter case, a leak proof inlet and a leak proof outlet can be disposed on the side wall of the EPD tank such that the flexible and movable conductive web can enter and exit the EPD slot without leakage, respectively.

In some embodiments, the permeate that permeates the colloidal particle template by the EPD device in step (2) may be a metal ion capable of undergoing a redox reaction, for example, Ni ²⁺ , a ceramic such as ZnO, or a polymerization. Things. Other materials such as graphite, CeO ₂ , TiO ₂ , Cu ₂ O, RuO ₂ may be used. Metals such as Ru, Cu, Ti, Al, Au, Ag, Pt, etc. can be used to carry out the redox reaction. An ethanol solution can be used as the EPD solution. The reaction time can be determined based on the electric field strength, for example, about 10 seconds to 1 hour. The pH can be determined based on the formulation, for example about 4-9. The solution may be isopropyl alcohol (IPA), acetone (ACE) or the like, or a similar organic solvent as long as it does not cause corrosion to the colloidal particles. Water (H ₂ O) can also be used, but its pH may need to be adjusted and the electric field should not be too strong (eg less than 2.5 volts/cm).

Depending on the composition of the colloidal particle template, the colloidal particle template in step (3) can be removed using different methods and apparatus. In some embodiments, a colloidal device can be used to thermally remove the colloidal particle template by heating the colloidal particle template of the permeate at about 500 ° C for 1 to 24 hours while retaining the permeate completely. The material used may be PS or PMMA. For organic materials, high temperature removal can be used; for colloidal templates made of inorganic materials such as SiO ₂ or ZnO, chemical removal (eg Buffered Oxide Etchant (BOE)) can be used. . In some other embodiments, a chemical etching apparatus can be used, wherein the colloidal particle template that transports the permeate is immersed in an etching solution (eg, 0.01-3 M ethyl acetate) disposed in an etching bath. The colloidal particle template is removed by chemical etching while still retaining the permeate completely.

In some embodiments in which a chemical etching apparatus is used in step (3), a flexible and movable conductive tape that carries the colloidal particle template and the permeating substance can be used and can be disposed through the etching. One of the leakage preventing inlet and the leakproof outlet on the side wall of the groove enters and exits the chemical etching device.

In some embodiments, the method can further include the step of separating the osmotic material from the flexible and movable conductive tape after the step (3) to obtain the porous film. For example, a split knife may be disposed between the web and the porous membrane to separate them such that the porous film forms a roll of film at the first spool and the second spool is used to recover the web.

Compared to existing methods of fabricating porous materials such as metal foams and nanoporous materials, the methods disclosed herein may have one or more of the following advantages: 1) large size highly porous materials having large relative surface areas are achieved . 2) The materials (e.g., porous membranes) may have atomic-array-like structures with densely packed pores or randomly distributed pores arranged neatly. In some examples, a nanoporous material having a fine-array porous structure can be achieved.

The highly porous material/film produced can have a pore size of from about 100 nm to about 5 mm and a grain domain of from about 5 microns to about 5 mm. The grain regions can be observed by an optical microscope (OM) to form regions of a periodic or quasi-periodic structure. Defects similar to grain boundaries may exist between the grain regions. The grain boundaries between the grain regions can provide a primary source of mechanical strength for the porous films.

The methods disclosed herein can be used to produce large area giant porous films having a size greater than 20 cm x 20 cm, having a thickness of, for example, about 10 cm (depending on the size of the colloidal particles). A substantial surface area to volume ratio can be achieved, which can be expressed as:

……………………………………(1)

among them, For specific surface area, d is the average pore diameter (in millimeters) and θ is the porosity. For example, for d = 0.01 mm, 74% porosity, the specific surface area may be about 4100 / mm; for d = 0.001 mm, the specific surface area may be about 41000 / mm.

In some embodiments, a bulk porous material having a three dimensional (3D) structure can be fabricated. It is compared to a porous material manufactured by an existing method. Existing metal foams generally have a pore size greater than 500 microns, and a specific surface area of from about 14 to about 3100 per millimeter, and have large pore size variations (such as greater than 100%).

Thus, the method disclosed herein has the advantage that the metal films produced are particularly suitable for use in catalysis and other applications requiring materials having large relative surface areas. Moreover, advantageously, some of these methods may be unrestricted by the melting point of the metal/alloy used to make the metal foam, and thus may be used to fabricate any fine array porous membrane utilizing metal ions capable of undergoing redox reactions. Furthermore, the purity of the metal component in some of the metal films produced can be as high as 99.99%, which is an advantage not obtained by the metal foam produced by the conventional manufacturing method because the conventional manufacturing method is in the process of melting the metal. In the middle, impurities are often produced. This advantageous feature also greatly increases the efficiency of the catalytic reaction.

In some embodiments, the porous material (eg, fine array porous membrane) may have a specific surface area greater than 10/mm, in some embodiments greater than 3100/mm, or in some embodiments, greater than 4100/mm (such as about 4108 / mm, about 8217 / mm, or about 41087 / mm). At the same time, the holes in these materials have a substantially uniform size, such as a standard deviation representing less than 20% of the amount of change, or less than 10% in some embodiments.

Furthermore, in the manufacture of materials having a giant porous structure, some of these methods are visibly elastically adjustable, which can use various deposition/infiltration methods such as electrodeposition, PVD (physical vapor deposition), CVD (Chemical Vapor Deposition), Sol-Gel (Sol-Gel Method), and chemical plating (such as electroplating, electroless plating) to infiltrate various materials such as metals, large molecular weight polymers, and ceramics. The process of preparing porous materials of various pore sizes is made more convenient by simply adjusting the size of the particles used to make the colloidal particle templates that are subsequently discarded.

Materials having different shapes and sizes can be conveniently fabricated by selecting working electrodes of assembly devices having different shapes and sizes. By using a flexible and movable conductive tape, the degree of automation and manufacturing efficiency in the process of manufacturing the porous materials can be greatly improved. The large-sized porous material having a densely packed periodic fine array porous structure in some embodiments disclosed herein can have excellent mechanical, acoustic, thermal, optical, electrical, and chemical properties, and thus can be used in various applications, such as catalysts. , dialysis membrane, heat exchange, energy storage, filtration, and tissue engineering.

In another aspect, an application system comprising the porous material described above is provided, wherein the system is designed as one of a desalination device, an ultra-micro bubble generation system, a capacitor system, or a battery system.

Some methods of making highly porous materials can be complex and expensive, and can be difficult to produce high purity porous materials with high specific surface areas.

Figure 1 illustrates a microstructure of a metal foam comprising interconnected metal of metallic ligaments 101 having different lengths and orientations and between adjacent metal ligaments. Individual voids (holes) 100 of different shapes and sizes are formed. Typical metal foam pore sizes can range from 0.5 to 8 mm.

In addition to the specific area, the uniformity of the hole size is another important factor. As shown in Fig. 1, the variation of the pore size of the conventional metal foam is as high as 100% or more.

In some embodiments disclosed herein, a manufacturing system can produce a porous material having superior properties. The system can include: a colloidal particle template forming portion designed to produce a colloidal particle template; a permeate portion designed to infiltrate a permeate material into the colloidal particle template; and a template removal portion designed to be removed The colloidal particles template and retain the permeate substantially completely.

2 illustrates a first step flow for fabricating a fine array of porous materials using the system in some embodiments. The manufacturing step may include: step (1), surface charged particle deposition to form an array (assembly process); step (2), deposition/infiltration; and step (3), template removal. The system can include a number of portions (e.g., a plurality of modules) 310, 320, 330 that implement the steps, respectively. A movable conductive tape can be used to transport the colloidal particle template between the watertight inlet and outlet of each of the channels. The portions 310, 320, 330 may have the functionality shown in Figure 3, and the details thereof are as follows.

Figure 3 illustrates a system which, in some embodiments, is designed to fabricate a large area, fine array porous membrane. The system can include an electrophoretic portion 310, a deposition/permeation portion 320, and a colloidal particle template removal portion 330.

The electrophoresis portion 310 can include an electrophoresis tank 311, a power supply 312, a reference electrode 313, a working electrode 314, a magnet stirrer 315, a leak proof inlet 316, and an oven/real time analyzer (Real Time Analyzer, Referred to as RTA) 319. An electrophoresis solution 317 comprising a suspended monodisperse colloidal nanosphere can be disposed in the electrophoresis tank 311; the leakage prevention inlet 316 can be disposed on a sidewall of the electrophoresis tank 311; the working electrode 314 can include a movable a continuous conductive tape 318 designed to enter the electrophoresis tank 311 via the leak-proof inlet 316, providing a surface for forming a colloidal particle template in the electrophoresis tank 311, if the colloidal particle template is electrophoresed Once the assembly has been completed, the electrophoresis tank 311 is removed, and the colloidal particle template is conveyed through the oven/RTA 319 for drying.

The deposition/permeation portion 320 can include a deposition tank 321, a power supply (not shown), a DC power supply, a reference electrode 323, a working electrode 324, a leak-proof inlet 325, and a leak-proof outlet 326. An electrodeposition solution 327 can be disposed in the deposition/permeation tank 321 . The leak-proof inlet 325 and the leak-proof outlet 326 may be respectively disposed on opposite side walls of the deposition tank 321 .

The working electrode 324 is located at an electrode position, and the suspension 327 is disposed in the deposition tank 321 and filled to cover the electrode position. The web from the electrophoresis portion 310 and carrying the dried colloidal particle template can enter the deposition tank 321 via the leak-proof inlet 325. A surface for forming a fine array of the porous film on the colloidal particle template may be provided in the deposition tank 321. Until the deposition of the fine array porous membrane is completed, the web can be removed from the electrodeposition tank 321 via the leak-proof outlet 326.

The colloidal particle template removing portion 330 may include an etching groove 331, a leakproof inlet 332, and a leakproof outlet 333. An etching solution 334 can be disposed in the etching bath 331. The leakage preventing inlet 332 and the leakage preventing outlet 333 may be respectively disposed on opposite side walls of the etching groove 331. The colloidal particle template and the fine array porous membrane are transported and the web from the deposition portion 320 can be moved into the etching bath 331 via the leak-proof inlet 332 to remove the colloidal particle template. After the etching of the colloidal particle template is completed, the web can be removed from the etching bath 331 via the leak-proof outlet 333. After the tape exits the etched groove 331, the fine array porous film 335, which is considered to be the porous material or film of the claimed embodiment, can be separated from the continuous conductive tape.

For example, a splitting blade (not shown) may be disposed between the conductive web 337 and the porous film 335 to separate them such that the porous film 335 forms a roll at a first reel (not shown). And a second reel (not shown) is used to recover the reel 337.

In some embodiments, the apparatus shown in Figure 3 can be used to fabricate a Nickel film having a fine array of porous structures. The process may include, for example, 1) preparing a monodisperse polystyrene (PS) colloidal suspension; 2) assembling a PS colloidal particle template; 3) performing nickel electrodeposition; and 4) heating or using ethyl acetate Etching to remove the PS nanosphere template.

The fine array porous material of the present invention has a large specific surface area and a uniform height of pores therein, compared to a conventional metal foam having a relatively low specific surface area and a lack of pore size uniformity.

Table 1 below compares the parameters defined by the conventional metal foam with the fine array porous material of the present invention in the equation (1). As shown in Table 1, the specific surface area of the fine array porous material may be higher than 3130 / mm, such as higher than 4100 / mm. However, the fine array porous material may have a specific surface area of between 10/mm and 3130/mm, while still having excellent properties that are not available for metal foams for various applications. For example, in some embodiments, a fine array of porous materials having a specific surface area of >10/mm can have a very uniform pore size, such as a standard deviation of <20%, or even <10%.

Table 1

4A is a top view of an SEM image of a fine array of porous structures.

Figure 4B is a side view of an SEM image of the structure of Figure 4A.

Figure 4C is another side view of the SEM image of the structure of Figure 4A.

4D is a top view of an SEM image of one of the stacked nanospheres.

4E is a top view of a low resolution (200x) SEM image of the inverse structure, wherein the portion depicted by the thick line shows the grain boundaries forming the grain regions, which can provide the mechanical strength of the porous material.

Figure 4F is an enlarged view (500x) of the structure of Figure 4E.

Figure 4G is an enlarged view (2500x) of a higher magnification of the structure of Figure 4E.

In some embodiments, the apparatus shown in Figure 3 can be used to fabricate a fine array of porous ZnO membranes. For example, the manufacturing process may include: 1) preparing a monodisperse polystyrene (PS) colloidal suspension; 2) assembling a PS colloidal particle template, and drying the template in an atmosphere of about 90-100 ° C, for example, After about 30 minutes; 3) electrodeposition of ZnO with a Zn(NO ₃ ) ₂ plating solution at a constant current (for example, 1 mA/cm ² ) at a temperature of about 70 ° C; and 4) by at about 500 ° C The PS nanosphere template was removed by heating in an environment for less than 2 hours. Thus, a good array of porous ZnO films having controllable plurality of periodic layers can be fabricated.

In some embodiments, the colloidal particle template formed via the assembly process can be made of polystyrene (PS), SiO ₂ , PMMA (polymethyl methacrylate), or any spherical powder material, the particle size of which It is between about 100 nm and 5 mm, and the amount of change in diameter (e.g., standard deviation) is within about ± 20%, and most preferably within about ± 10%. For example, in some embodiments, the particle size is about 200 nanometers ± 40 nanometers; in another example, the particle size is about 300 nanometers ± 60 nanometers. The particles may be spherical and may be hollow or solid spheres. In some other embodiments, non-spherical shapes can also be used.

In some embodiments, the solution used has a pH in the range of 4-9, a temperature in the range of about -10 to 45 ° C, a DC electric field in the range of about 0.1 V/cm - 1 kV/cm, and an electrode tip. The electrode tip withdraw velocity ranges from about 100 nm/sec to 10 cm/sec.

In some embodiments, the bake temperature for removing the colloidal particle template can depend on the nanosphere material and can range from about ± 10% of the glass transition temperature of the material.

In some embodiments, the grain regions of the fine array porous membranes (planar/monolithic) may range from about 5 microns to 5 millimeters, and the pore size may range from about 100 nanometers to 5 millimeters. Within the scope.

In some embodiments, the density of the solution can be higher than the density of the nanospheres such that the nanospheres float on the solution. Alternatively, the density of the solution may be lower than the density of the nanospheres such that the nanospheres are uniformly dispersed in the solution, wherein the liquid may be selected based on density.

In some embodiments, the assembly device can have a vertical configuration so that the thickness of the film can be controlled and the film can be removed from the device.

The porous materials disclosed herein are useful in a variety of applications. For example, in some embodiments, a water purifier can use a filter core comprised of the porous material of the present invention. The filter can be a membrane, and the high surface area to volume ratio of the porous membrane as described above allows the contaminated water to be effectively purified.

In some other embodiments, a seawater desalination system can use a membrane having a high surface area to volume ratio. The membrane can aid in reverse osmosis or ion exchange processes for desalination of seawater.

In some other embodiments, an ultrafine bubble generating system can use a membrane having a high surface area to volume ratio. This porous structure can contribute to the generation of bubbles in various liquids.

In still other embodiments, a capacitor or a battery may use a porous material having a high surface area to volume ratio. The large surface area provided by the porous material of the present invention allows a capacitor to have a higher capacitance or a higher ion exchange rate of a battery to improve cell efficiency.

In some other embodiments, the porous materials can be used in applications such as vibration and sound absorption, impact protection, heat exchange, membranes, filtration, ion exchange, photon, gas sensing, catalysis, biomedical engineering, and the like.

However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.

100‧‧‧Individual gaps (holes)
1~3‧‧‧Steps
101‧‧‧Connective tissue of metal ligament
310‧‧‧ Electrophoresis section
311‧‧‧electrophoresis tank
312‧‧‧Power supply
313‧‧‧ reference electrode
314‧‧‧Working electrode
315‧‧‧Magnetic mixer
316‧‧‧ leak proof entrance
317‧‧‧ Electrophoresis solution
318‧‧‧Continuous Conductive Tape
319‧‧‧Oven/Real Time Analyzer
321‧‧‧deposition tank
320‧‧‧Deposition/infiltration section
323‧‧‧ reference electrode
324‧‧‧Working electrode
325‧‧‧ leak proof entrance
326‧‧‧ leak-proof exit
327‧‧‧electrodeposition solution
330‧‧‧Colloid particle template removal part
331‧‧‧etching groove
332‧‧‧ leak proof entrance
333‧‧‧ leakproof exit
334‧‧‧etching solution
335‧‧‧Microarray porous membrane
337‧‧‧Electrical tape

Other features and effects of the present invention will be apparent from the embodiments of the drawings, in which:

Figure 1 illustrates an OM (optical microscope) image of a metal foam.

2 is a flow chart of one method of making a conventional porous material.

Fig. 3 is a schematic view showing an embodiment of a system for manufacturing a large-sized giant porous membrane using a flexible and movable conductive tape as a working electrode.

4A is a top view of an SEM image of a fine array of porous structures.

Figure 4B is a side view of an SEM image of the structure of Figure 4A.

Figure 4C is another side view of the SEM image of the structure of Figure 4A.

4D is a top view of an SEM image of one of the stacked nanospheres.

4E is a top view of a low resolution (200x) SEM image of the inverse structure, wherein the portion depicted by the thick line shows the grain boundaries forming the grain regions, which can provide the mechanical strength of the porous material.

Figure 4F is an enlarged view (500x) of the structure of Figure 4E.

Figure 4G is an enlarged view (2500x) of a higher magnification of the structure of Figure 4E.

Claims (21)

A porous material comprising a specific surface area greater than 10/mm, the specific surface area being dependent on different pore sizes, wherein the porous material comprises a plurality of pores having a substantially uniform size and a variation of less than about 20%, wherein The size is greater than about 100 nanometers and less than about 5 millimeters, wherein the porous material comprises a plurality of grain regions that increase the mechanical strength of the porous material, the grain regions having a size of from 5 micrometers to 5 millimeters. The porous material according to claim 1, wherein the porous material is a substrateless film. The porous material of claim 1, wherein the specific surface area is greater than 4100 / mm, wherein the dimensional change is less than about 10%. A system designed to produce a porous material, the system comprising: a particle template forming portion designed to produce a particle template by electrophoresis; a permeate portion designed to infiltrate a permeate into the particle template; a template removal portion designed to remove the particle template and substantially retain the permeate substantially, thereby forming a substrateless porous material having a specific surface area greater than 10/mm, wherein the porous material comprises a plurality of a void having a dimension that is substantially uniform and varying by less than about 20%, wherein the dimension is greater than about 100 nanometers and less than about 5 millimeters; wherein the porous material comprises a plurality of materials for increasing the mechanical strength of the porous material The grain area has a size of 5 micrometers to 5 millimeters. The system of claim 4, further comprising a baking portion, the baking portion It is designed to dry the particle template produced through the particle template forming portion, thereby increasing the mechanical strength of the particle template. The system of claim 5, wherein the particle template forming portion comprises an electrophoresis assembly device comprising: an electrophoresis tank; a DC power supply; a magnet agitator; a reference electrode; An electrode; wherein: an electrophoresis solution comprising suspended particles is disposed in the electrophoresis tank; the reference electrode and the working electrode are substantially vertically disposed in the electrophoresis tank; and the working electrode is provided for electrophoretically manufacturing One of the surface of the particle template. The system of claim 6 wherein the reference electrode is cylindrical and disposed adjacent to a gas-liquid interface or below about 0-5 cm below the interface. The system of claim 7, wherein the working electrode comprises a flexible and movable conductive tape, and a leak-proof inlet is disposed on one side wall of the electrophoresis tank, thereby being flexible and A moving conductive tape can enter the electrophoresis tank. The system of claim 4, wherein the infiltration portion comprises an electrophoretic deposition (EPD) device, the electrophoretic deposition device comprising: An electrophoretic deposition tank; a continuous current power supply; a reference electrode; and a working electrode; wherein: an electrophoretic deposition solution is placed in the electrophoretic deposition bath; and the working electrode is designed to transport the colloidal particle template, the colloid A particle template provides a surface for electrophoretical deposition of the osmotic material onto the colloidal particle template within the electrophoretic deposition bath. The system of claim 4, wherein the template removing portion comprises a chemical etching device comprising an etching groove internally provided with an etching solution, whereby the colloidal particle template is removed by the etching solution And only retain the permeate. The system of claim 10, wherein a leak-proof inlet and a leak-proof outlet are provided on the side wall of the etching tank and are used to convey the colloidal particle template and the permeable substance to be flexible and movable. The conductive tape can enter and exit the etching groove separately without leakage. The system of claim 11 further comprising a split knife designed to separate the permeate from the flexible and movable conductive web to obtain the porous material and recover the flexibility And a movable conductive tape. A method for producing a porous material, comprising the steps of: (1) forming a portion by a particle template, and forming a particle template by electrophoresis; (2) infiltrating a permeate into the particle template by a permeating portion; And (3) removing the portion by a template, removing the particle template, and completely retaining the permeate, thereby forming a substrate-free porous material having a specific surface area greater than 10/mm, wherein the porous material comprises a plurality of pores having a size substantially uniform and varying by less than about 20%, wherein the size is greater than about 100 nanometers and less than about 5 millimeters; wherein the porous material comprises a plurality of layers for increasing the porous material A grain region of mechanical strength having a size of from 5 micrometers to 5 millimeters. The method of claim 13, further comprising, after the step (1) and before the step (2), immediately baking the particle template to increase the mechanical strength of the particle template, wherein the baking step It is carried out at a temperature of about 90 to 500 ° C and a relative humidity of more than 75 for about 0.5 to 2 hours. The method of claim 14, wherein: an electrophoresis solution comprising suspended colloidal particles is disposed in an electrophoresis tank; a reference electrode and a working electrode are substantially vertically disposed in the electrophoresis tank; the reference electrode a cylindrical shape; the working electrode is provided for electrophoretically fabricating one surface of the particle template; and an electric field between the reference electrode and the working electrode is in a range of about 0.1 V/cm to 1000 V/cm. The method of claim 15, further comprising providing the suspended particles comprising a powder material selected from at least one of polystyrene, ceria, or polymethyl methacrylate, wherein The powder material has a particle size of from about 100 nm to about 5 mm, and wherein the electrophoretic solution includes an ionic solution designed to provide a charge to the surface of the colloidal particles. The method of claim 16, wherein the electrophoresis solution comprises at least one of an ethanol solution having a pH of about 4-9, ammonia/nitric acid, or sodium dodecyl sulfate (SDS). The method of claim 17, wherein the working electrode is stationary or is designed to move at a speed of between about 100 nm/sec and 10 cm/sec. The method of claim 13, further comprising: heating the particle template of the permeate to a temperature of about 500 ° C for less than 24 hours, whereby the particle template is thermally removed while substantially retaining the permeate substantially, wherein The particle template comprises a polymer. The method of claim 14, further comprising chemically removing the particle template while substantially completely retaining the permeate, and wherein the chemical removal step comprises etching about 1 at a temperature of about 40-80 ° C. -4 hours. A system comprising the porous material of claim 1, wherein the system is designed as one of a desalination system, an ultrafine bubble generating system, a capacitor system, or a battery system.