阅读说明：本技术 用于制造具有改性表面且由金属制成的开孔成型体的方法以及使用该方法制造的成型体 (Method for producing open-porous molded bodies having modified surfaces and made of metal, and molded body produced using said method ) 是由 T·布特内尔 G·沃尔特 汉斯-迪特里希·博姆 T·韦斯加伯尔 B·基巴克 克里斯蒂安·I 于 2018-09-14 设计创作，主要内容包括：本发明涉及一种用于制造具有改性的表面并且由金属制成的开孔成型体的方法。所述成型体用作半成品部件,由金属制成的开孔成型体的表面涂覆有金属的化合物的颗粒,其中该颗粒可以在热处理中还原或热分解或化学分解,并通过热处理产生相应金属的颗粒,所述颗粒通过化学还原或热分解或化学分解获得。在涂覆过程之后,进行至少一热处理,在该热处理中,产生的金属颗粒通过烧结颈或烧结桥连接至半成品产品的表面和/或产生的相邻的颗粒,使得所获得的开孔成型体的比表面积增大到至少30m<Sup>2</Sup>/l,和/或与未涂覆的金属半成品产品的起始材料相比增大到至少5倍。(The invention relates to a method for producing open-porous molded bodies having a modified surface and made of metal. The shaped body is used as a semi-finished part made ofThe surface of the open-porous shaped body made of metal is coated with particles of a compound of the metal, wherein the particles can be reduced or thermally decomposed or chemically decomposed in a heat treatment, and particles of the corresponding metal are produced by the heat treatment, the particles being obtained by the chemical reduction or thermal decomposition or chemical decomposition. After the coating process, at least one heat treatment is carried out in which the metal particles produced are connected to the surface of the semifinished product and/or adjacent particles produced by means of sintering necks or bridges, so that the specific surface area of the open-porous shaped body obtained is increased to at least 30m 2 /l, and/or increased by at least a factor of 5 compared to the starting material of the uncoated semi-finished metal product.)

1. A method for producing a metal-comprising open-porous shaped body with a modified surface, wherein, on the surface of the metal-comprising open-porous shaped body as a semi-finished component, particles of a metal compound are coated, which can be reduced or thermally decomposed or chemically decomposed in a heat treatment and form particles of the corresponding metal obtained by chemical reduction or thermal decomposition or chemical decomposition;

and

after the coating operation, at least one heat treatment is carried out, in which the formed metal particles are bonded to the surface of the semifinished part and/or to the formed adjacent metal particles by sintering necks or sintering bridges, so that

The obtained opening isThe specific surface area of the shaped body is increased to at least 30m²And/or increased by a factor of at least 5 compared to the starting material of the uncoated semi-finished metal part.

2. The method of claim 1, wherein particles of said compound of a metal are used as a powder, powder mixture and/or suspension/dispersion.

3. Method according to claim 1 or 2, characterized in that the application of the particles of the compound in the form of a powder, a powder mixture and/or a suspension/dispersion of the metal is performed by dipping, spraying, in a pressure-assisted manner, electrostatically and/or magnetically.

4. A method according to any one of claims 1 to 3, characterized in that an organic and/or inorganic binder is used in the form of a solution, suspension/dispersion or in the form of a powder to improve the adhesion of the particles.

5. The method according to any one of claims 1 to 4, characterized in that the application of the particles of the compound of the metal is repeated a plurality of times, in particular at least three times.

6. Method according to any one of claims 1 to 5, characterized in that, in the case of multiple coating with particles of the compound of the metal, when using a binder, the application of the binder is repeated multiple times, in particular at least three times.

7. The method according to any one of claims 1 to 6, characterized in that the application of the binder and the application of the particles of the metal compound are carried out using different amounts on different sides of the surface of the semi-finished component, in particular on surfaces facing each other, so that in each case different porosities, pore sizes and/or specific surface areas are obtained on differently arranged surface areas.

8. Method according to any of the preceding claims, characterized in that Ni, Fe, Cr, Al, Nb, Ta, Ti, Mo, Co, B, Zr, Mn, Si, L a, W, Cu, Ag, Au, Pd, Pt, Zn, Sn, Bi, Ce or Mg are used as metal for the semi-finished part and particles to be applied, or

Compounds of Ni, Fe, Cr, Al, Nb, Ta, Ti, Mo, Co, B, Zr, Mn, Si, L a, W, Cu, Ag, Au, Pd, Pt, Zn, Sn, Bi, Ce or Mg, in particular salts, oxides, nitrides, hydrides, carbides, sulfides, sulfates, fluorides, chlorides, bromides, iodides, phosphates, azides, nitrates, amines, amides, metal-organic complexes or metal-organic complexes are used as metals for reducible, thermally decomposable or chemically decomposable compounds.

9. Method according to any one of the preceding claims, characterized in that a semi-finished component is used which is obtained by electrochemical coating of an open-porous body of polymer material with a corresponding metal.

10. Open-porous shaped body produced by the method according to any one of the preceding claims, characterized in that the shaped body with metal particles bonded by sintering necks or sintering bridges to the surface of the semi-finished component and/or to the surface of adjacent particles has at least 30m²Specific surface area/l.

11. Shaped body according to the preceding claim, characterized in that the pore size in the coated and sintered open-porous shaped body corresponds to at most 10000 times the used particle size of the metal compound.

12. Shaped body according to any of the two preceding claims, characterized in that no more than 3 mass%, preferably no more than 1 mass% of oxygen is present in the material of the shaped body.

Technical Field

The invention relates to a method for producing open-porous molded bodies or open-porous molded bodies comprising metal having a modified surface, and to the molded bodies produced by the method.

Background

In particular, it is known to coat the surface of a porous metal shaped body in order to improve its properties. For this purpose, use is generally made of a pulverulent material which is applied to the surface of the shaped body by means of a binder or suspension and in a heat treatment removes organic constituents and can then form, at elevated temperature, a coating or surface region on the surface of the shaped body which has a different chemical composition than the material from which the shaped body is made.

The specific surface area of the shaped bodies can also be increased by these known possibilities, but this is only possible to a limited extent by the known possibilities.

However, very large specific surface areas are advantageous for many industrial applications and are highly desirable in electrodes, for example in catalytic assisted processes, filtration or electrochemical applications.

Furthermore, in respect of the properties of the surface of the open-porous shaped body of interest, it is often also desirable to influence other properties of the surface.

Disclosure of Invention

It is therefore an object of the present invention to provide an open-porous shaped body which is composed of a metal material and can have an increased specific surface area and other surface properties than those which can be achieved by the base material from which the open-porous shaped body after surface modification is produced.

According to the invention, this object is achieved by a method having the features of claim 1. Claim 10 relates to a shaped body produced by the process. Advantageous embodiments and further developments can be achieved by means of the features indicated in the dependent claims.

In the present invention, an open-pore formed body composed of a metal material is used as a semi-finished member. These open-porous shaped bodies can be metal grids, metal meshes, metal fabrics, metal foams, metal wool or semi-finished parts comprising metal fibers.

Advantageously, however, the semifinished part can also be an open-pored shaped body of the following type: in the open-porous shaped body, the polymer material has been electrochemically coated with a metal. The semifinished parts produced in this way can be subjected to a heat treatment in which the organic constituents of the polymer are removed by pyrolysis. However, this removal of the organic component may also occur later in time with the removal of the binder, which will be discussed in more detail below.

In one embodiment of the invention, the open-porous shaped body is coated with particles of a compound of the metal on the surface of the open-porous shaped body comprising the metal that has been obtained before or after the heat treatment. Here, the particles should also be introduced into the interior of the shaped body, i.e. into the pores or interstices of the semifinished part.

The particles of the compound of the metal may be used as a powder, powder mixture, suspension or dispersion for a coating operation. The coating of the surface of the semifinished part with the powder, powder mixture and/or suspension/dispersion can be carried out by dipping, spraying, pressure-assisted, electrostatically and/or magnetically.

In a further alternative according to the invention, the powder, powder mixture, suspension or dispersion for coating the open-porous semifinished part may comprise not only metal compound particles but also inorganic and/or organic binders which are mixed into the powder, powder mixture, suspension or dispersion as solid powder in the form of fine particles or which are present in dissolved form in the liquid phase of a solution, suspension/dispersion of metal particles or metal compound particles.

The coating of the surface of the semi-finished part with the binder in the form of a solution or a suspension/dispersion can be achieved by dipping or spraying. The open-porous shaped body thus prepared as a semi-finished part is coated with a powder of a compound of a chemical element. The powder comprises a compound which can be converted into a metal by chemical reduction or thermal decomposition or chemical decomposition in a thermal treatment.

The distribution of the powder particles on the surface which has been wetted with the liquid binder and the adhesion of the particles to the surface can be improved by the action of mechanical energy, in particular vibration.

The application of the particles as powder, powder mixture and/or suspension/dispersion can be repeated a plurality of times, preferably at least three times, particularly preferably at least five times. This also applies in each case to the vibrations to be carried out and optionally to the application of the adhesive.

However, it is also possible to coat the surface of the semifinished part before the heat treatment in which the organic constituents of the polymer material by means of which the semifinished part has been manufactured are removed. After the application of the material containing the particles, a thermal treatment is carried out in which the organic and volatile constituents of the polymer material are removed and at the same time any binder used is removed.

After the heat treatment and the application of the particles, a sintering is carried out in which sintering necks or sintering bridges are formed between the particles of the metal particles, which are formed in the heat treatment and have been formed in the reduction or decomposition, and the metal surface of the open-porous metal shaped body.

Here, the specific surface area of the open-porous shaped body which has been coated and sintered in this way should be increased to at least 30m²The specific surface area is increased by a factor of at least 5 compared to the starting material of the uncoated metal shaped body as a semifinished part.

Here, depending on the application, a pore size in the range of 450 μm to 6000 μm and 1m²/l-30m²The porous basic skeleton of the specific surface area/l should be filled with particles from one side (porosity gradient) or completely (particle size d)₅₀In the range of 0.1 μm to 250 μm) or the pillars of the porous metal shaped body should have been coated on the surface.

In order to obtain different porosities, pore sizes and/or specific surface areas in each case, the particle coating can be carried out with different amounts on different sides of the surface, in particular on surfaces of the semifinished part which are arranged opposite one another. This can be achieved, for example, by applying different amounts of particles (with or without the use of a binder) as a powder, a powder mixture or in the form of a suspension/dispersion on surfaces arranged on different sides. In this way, it is also possible to achieve a gradually changing form of the shaped bodies produced according to the invention.

The pore size in the applied particle layer of the coated and sintered open-porous shaped body corresponds to not more than 10000 times the particle size used. This may also be additionally influenced by the maximum sintering temperature and the holding time at this temperature, since with increasing temperature and holding time the mass transfer through diffusion and thus sintering, which is associated with a reduction in the pore volume, is promoted.

The material from which the shaped bodies produced according to the invention are made should contain not more than 3 mass%, preferably not more than 1 mass%, of O₂. For this purpose, an inert or reducing atmosphere is preferably provided while carrying out a heat treatment for removing organic constituents, sintering and/or optionally a chemical reduction to be carried out.

In thermal or chemical decomposition, suitable atmospheric conditions may be selected for each decomposition process. Thus, the heat treatment may be carried out in an inert atmosphere (e.g. an argon atmosphere), under vacuum conditions or in a reducing atmosphere (which, for example, contains hydrogen), wherein, for example, unnecessary decomposition products are removed.

The method can also comprise the following steps: (i) the use of such open-porous shaped bodies produced according to the invention in the filtration field, (ii) the use of such open-porous shaped bodies produced according to the invention as catalysts (for example in the synthesis of ethylene oxide using Ag foam catalysts coated with Ag particles), (iii) the use of such open-porous shaped bodies produced according to the invention as electrode materials, or (iv) the use of such open-porous shaped bodies produced according to the invention as supports for catalytically active substances.

In the case of application (i), increasing the specific surface area leads to better filtration performance, since the adsorption tendency and adsorption capacity increase significantly.

In application (ii), the increase in specific surface area leads to a greater proportion of the catalytic activity, since not only the number of active sites increases, but the surface also has a distinctly faceted structure. The resulting increased surface energy also leads to a significant increase in catalytic activity compared to the non-faceted surface of the starting open-celled shaped body.

In the case of application (iii), the increase in the specific surface area likewise leads to an increase in the active centers, which, in combination with the faceted structure of the surface, leads to a significant reduction in the electrical overvoltage compared with commercial electrodes (e.g. nickel or carbon). As a specific application, electrolysis may also be mentioned, for example using Ni or Mo foam coated with Ni or Mo particles. In particular, in this application, sintered metal open-porous shaped bodies coated on one side with metal particles can also be used advantageously, since in this case the gradual change in the pore size ensures good transport away of the gas bubbles.

In the case of application (iv), the increase in specific surface area leads to better adhesion of the active ingredient (e.g. catalytic coating) to the support surface, which significantly improves the mechanical, thermal and chemical stability of the catalytic material.

Suitable metals to be applied for the granules and the semifinished parts, from which the shaped bodies produced according to the invention can be produced, are Ni, Fe, Cr, Al, Nb, Ta, Ti, Mo, Co, B, Zr, Mn, Si, L a, W, Cu, Ag, Au, Pd, Pt, Zn, Sn, Bi, Ce or Mg.

Compounds of the metals Ni, Fe, Cr, Al, Nb, Ta, Ti, Mo, Co, B, Zr, Mn, Si, L a, W, Cu, Ag, Au, Pd, Pt, Zn, Sn, Bi, Ce, Mg, V, which can be converted into particles of the corresponding metals by chemical reduction, thermal decomposition or chemical decomposition in the heat treatment, can be used, in particular, the oxides, nitrides, hydrides, carbides, sulfides, sulfates, phosphates, fluorides, chlorides, bromides, iodides, azides, nitrates, amines, amides, salts of metal-organic complexes, metal-organic complexes or decomposable salts thereof for the material comprising the particles, to which the surface of the open-porous shaped body present as a semifinished part is to be coated.

During thermal or chemical decomposition of the compound to produce the corresponding metal, an atmosphere suitable for decomposition (which may be inert, oxidative or reductive) is maintained until thermal or chemical decomposition of the compound to the metal has occurred. In order to chemically reduce the compound to the corresponding metal, preferably, the heat treatment causing the chemical reduction may be carried out in a reducing atmosphere, in particular in a hydrogen atmosphere, for at least a period of time until the chemical reduction has been carried out.

For chemical decomposition by oxidation, atmospheres containing oxygen, fluorine, chlorine, any mixture of these gases, and any mixture of inert gases such as nitrogen, argon, or krypton are particularly useful.

In the thermal or chemical decomposition of the respective compounds of the particle-forming metals, a similar process can be employed by maintaining suitable atmospheric conditions during the heat treatment, at least until the respective decomposition process has ended to a sufficient extent and sufficient metal particles for sinter-joining to the material of the semi-finished component have been obtained as a result of the decomposition.

In the case of chemical decomposition, the metal cations may be reduced to form elemental metals. However, the anionic component may be oxidized. It is also contemplated to chemically decompose a compound of a relatively noble metal in air (i.e., in a relatively oxidizing atmosphere) to yield the elemental metal (Au, Pt, Pd). Disproportionation according to illustrative equation 2GeI < - > Ge(s) + GeI (g) may also be performed for aluminum, titanium, zirconium, and chromium. It is also possible to use crystals, metal-organic complexes or salts thereof in which the metal center is already in the oxidation state 0.

The surface properties of the open-porous shaped bodies produced according to the invention can be influenced, for example, in terms of heat resistance, corrosion resistance, chemical resistance, adhesion of the catalytic washcoat and catalytic function, by the metal particles which have been formed and sintered to the surface of the semifinished part via chemical reduction, thermal decomposition or chemical decomposition. Here, the gradual transition between the metal material of the semifinished part and the material of the formed metal particles also has an advantageous effect. Here, the struts from the surface to the semifinished part can form different phases, as can also be seen from the working examples below.

The porosity, pore size and specific surface area may be substantially influenced by the morphology of the particles used for the coating. In order to achieve a high specific surface area and a fine pore structure, particles (e.g., electrolyte powder) having a small size and a dendritic shape are advantageous. Due to their irregular geometry, which does not allow a gapless arrangement, adjacent particles form voids that partially connect to form channels between the contact points and the particle bodies. Furthermore, when particles from the compound are used, additional micropore space left by volatile components is formed in the thermal or chemical decomposition. The greater the proportion of the volatile component of the compound and thus the greater the volume occupied, the higher the proportion of micropore space in the total pore volume. For coatings with metal oxide particles, it is therefore advantageous to use oxides having a high oxidation state and therefore a high proportion of oxygen. Since the sintering activity of the structure increases with increasing specific surface area, the atmosphere, the holding time and the sintering temperature in relation to the material are chosen such that the particles sinter to each other and to the semifinished part in a mechanically stable manner without significantly densifying the pores.

Detailed Description

The invention will be illustrated below by means of an example.

Working example 1

As working example 1, an open-cell formed body having an average pore diameter of 450 μm, a porosity of 95%, a size of 70mm × 63mm, and a thickness of 1.6mm, which was obtained by electrochemical coating of a porous foam composed of polyurethane, was subjected to a heat treatment to remove organic components, and was made of silver, as a semi-finished member.

Subsequently, the surface of the semifinished part from which the organic constituents have been removed is coated by spraying a suspension having the following composition:

-48% of<5 μm of Ag₂O a metal oxide powder, and a metal oxide powder,

-1.5% of a polyvinylpyrrolidone (PVP) binder,

49.5% of water as solvent,

-1% of a dispersant.

For this purpose, the pulverulent binder was first dissolved in water, then all the other ingredients were added and mixed in a Speedmixer at 2000rpm for 2 × 30 seconds to give a suspension.

The prepared powder suspension is sprayed on both sides of the semifinished part several times by a wet powder spraying process. Here, the suspension is atomized in a spraying device and applied to the surfaces on both sides of the semifinished part. The suspension is distributed evenly in the porous network of the semifinished part by the outlet pressure from the nozzle. The suspension adheres only to the surface of the pillars, so that the pillars are completely covered with the suspension and the open porosity of the semifinished part is largely retained. Subsequently, the semifinished parts coated in this way are dried in air at room temperature.

For binder removal, reduction and sintering, heat treatment is carried out under a hydrogen atmosphere and subsequently in a furnace. For this purpose, the furnace is heated at a heating rate of 5K/min. The reduction of silver oxide started below 100 ℃ and ended at 200 ℃ with a holding time of about 30 minutes under hydrogen. The remaining binder removal and sintering process may then be performed in an oxygen-containing atmosphere (e.g., air) at a temperature range of 200 ℃ to 800 ℃ for a time period of 1 minute to 180 minutes.

During this further heat treatment, the silver oxide is first reduced to metallic silver, which is present in the form of nanocrystals. As the residual binder is removed and the metallic silver particles are then partially sintered onto the silver foam struts, the particles grow to form larger, coarser crystal agglomerates, and secondly Ag also diffuses out of the powder particles and into the strut material until the powder particles are firmly bonded to the struts of the surface of the open-celled shaped body by the formed sintered necks or bridges.

After this further heat treatment, there is a homogeneous open-porous shaped body formed from 100% silver.

The porosity was about 93%.

The surface of the pillar has high roughness. The reason for this is that the applied powder particles are only bonded to the surface of the semi-finished component by the sintering neck/sintering bridge, so that the original particle morphology is retained. By carrying out this process, the internal specific surface area (measured by the BET method) of the open-celled shaped body of the finished product can be from the first 10.8m²Increase to the following 82.5 m/l (uncoated state)²L (state after coating).

Working example 2

Open-porous shaped bodies consisting of nickel, having an average pore diameter of 450 μm, a porosity of about 95%, a size of 200mm × 80mm, and a thickness of 1.6mm (produced by the electrolytic deposition of Ni on PU foam) with a mass of 15g and an average particle size MoS of < 60 μm were used as semi-finished components₂Powder, 20ml of a 1% strength aqueous solution of polyvinylpyrrolidone.

The semifinished part consisting of nickel is sprayed with a binder solution on one side, so that the previously opened pores are closed on one side by the binder. The semi-finished product moistened with adhesive is then fixed in a vibration device and MoS is spread on the side coated with adhesive₂And (3) powder. The pore space near the surface is completely filled with the agglomerate formation. Due to the vibration, the powder is also partially distributed to the interior of the semi-finished part. The underside of the semifinished product which has been coated in this way remains uncoated. Thus, the powder loading in the foam gradually changes from the upper side to the lower side.

The removal of the binder (removal of organic components) was performed in heat treatment under an argon atmosphere. For this purpose, the furnace is heated at a heating rate of 5K/min. The removal of the binder started at about 300 c and ended at 600 c with a holding time of about 30 minutes. Heating was then continued to 1100 ℃ and held at this maximum temperature for a period of 1 hour, wherein MoS₂Is decomposed into Mo and S and the sulfur in the gas phase is carried away by the argon stream. The atmosphere in the heat treatment was then switched from argon to hydrogen and heating was continued. The sintering process takes place from a temperature of 1260 ℃ and a holding time of 60 minutes.

During sintering, Mo diffuses out of the powder particles and into the pillar material until the powder particles are firmly bonded to the pillars of the semi-finished component by the formed sintered necks or bridges. However, a complete equalization of the element concentrations does not occur.

After this heat treatment, there are open-porous shaped bodies with gradually changing porosity and pore size. The side which had previously been wetted with binder and provided the applied powder, had a porosity of < 30% and a pore size in the range of 5 μm to 50 μm and continued to increase to 95% porosity on the uncoated side of the shaped body and a pore size of 450 μm.

The molybdenum-coated foam struts had a gradually changing phase composition as follows:

composition/phase: mo (porous layer outside the pillar and in the filled pore space)

MoNi (outer transition zone)

MoNi₃(Central transition zone)

MoNi₄(internal transition region)

Ni (inside of pillar)

The surface of the pillar has high roughness. The reason for this is that the applied powder particles are only bonded to the supporting foam by the sintering necks or bridges, so that the original particle morphology is retained.

Working example 3

Open-pored shaped bodies consisting of nickel and having an average pore diameter of 580 μm, a porosity of about 95%, a size of 75mm × 70mm, a thickness of 1.9mm (produced by electrodeposition of Ni on PU foam) and a mass of 12g were used as semi-finished components<Titanium hydride TiH with an average particle size of 45 μm₂Powder, mass 0.12g having<An average particle size of 80 μm of stearamide wax was used as the powder, and a 1% strength aqueous solution of polyvinylpyrrolidone of 20ml in volume was used as the binder.

The powder and stearamide wax were mixed for 10 minutes using a Turbula mixer.

The adhesive solution is sprayed on both sides of the semifinished part. The semi-finished part is then fixed in a vibrating device and titanium hydride powder is sprinkled on both sides. Due to the vibration, the powder is distributed in the porous network of the semi-finished part. The coating with the binder and the powder was repeated five times so that the pore space had been completely filled. The semifinished parts which have been treated in this way are subsequently dried in air at room temperature.

The removal of the binder is performed under hydrogen atmosphere. For this purpose, the furnace is heated at a heating rate of 5K/min. The removal of the binder started at about 300 c and ended at 600 c, holding at this temperature for about 30 minutes. Then, decomposition of the titanium hydride into hydrogen and titanium was carried out in a heat treatment at 700 ℃ for 60 minutes under vacuum. Followed by further heating to a sintering temperature of 900 c for a holding time of 30 minutes.

After the heat treatment leading to sintering, the pillars of the semi-finished component which have been coated with titanium hydride have a gradually changing phase composition as follows:

composition/phase: ti (porous layer outside the pillars and in the filled pore spaces)

Ti₂Ni (outer transition zone)

TiNi (Central transition zone)

TiNi₃+ TiNi (internal transition zone)

Ni (inside of pillar)

The open-porous shaped body which had been treated in this way had a porosity of 48% and a specific surface area of 55m²/l。