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Title:
NOVEL PRODUCTION METHOD AND USE OF NEW NANO-METAL AND METAL-CERAMIC COMPOSITE CATALYSERS
Document Type and Number:
WIPO Patent Application WO/2015/191018
Kind Code:
A1
Abstract:
The present invention relates to production of activated stabilized nano metal powders used in the synthesis of nano metal composites or in the synthesis of dyes which are metal complexes of the type Phtalocyanine, Naphtalocyanine, Porphyrazine, Porphyrine, sub-Phtalocyanine, sub-Naphtalocyanine, sub-Porphyrazine and sub-Porphyrine and in the synthesis of the other probable organic dyes, and the present invention relates to production of nano metal composites of these dyes by using mechanochemical roll-milling method.

Inventors:
OLGUN UGURSOY (TR)
Application Number:
PCT/TR2015/050008
Publication Date:
December 17, 2015
Filing Date:
June 12, 2015
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
OLGUN UGURSOY (TR)
International Classes:
B22F1/14; B22F1/145; B22F9/04; B22F1/054
Domestic Patent References:
WO2007136757A22007-11-29
Foreign References:
CN101829777A2010-09-15
US20130118064A12013-05-16
US20110021360A12011-01-27
Other References:
None
Attorney, Agent or Firm:
KAYA, Erdem (Senyurt Is Mrk. No: 6 D:8 Nilüfer, Bursa, TR)
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Claims:
CLAIMS

1 A method for bringing a mixture, comprising at least one metal (M) powder or metal- ceramic composite catalyser, into nano particle dimensions, characterized by comprising the step of providing roll-milling of a mixture inside at least one metal pipe.

2. A method according to Claim 1 , characterized in that a chemical reaction takes place thanks to at least one organic compound provided inside said metal pipe. 3. A method according to Claim 2, characterized in that said reaction takes place in the presence of at least one organic compound, polymer or dye, and thereby metal is coated.

4. A method according to Claim 1 , characterized in that the metal is selected from Li, Na, K, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu,

Ag, Au, Zn, Cd, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Se, Te.

5. A method according to Claim 1 , characterized in that metal is in metal oxide form or in ceramic form.

6. A method according to Claim 5, characterized in that metal oxide is selected from Al203, ZnO, Ti02, Si02, MgO, B203, Zeolite and hydroxyapatite.

7. A method according to Claim 1 , characterized in that the metal is in metal salt form.

8. A method according to Claim 7, characterized in that the metal salt is selected from F, CI, Br, I, CH3COO-, S042-, C2042", P043", N03", OH", C032", HCO3", H2PO4 ", HPO42" salts. 9. A method according to Claim 1 , characterized in that the mixture comprises organic substance.

10. A method according to Claim 1 , characterized in that the organic substance is phthalonitrile or naphthalonitrile.

1 1. A method according to Claim 2, characterized in that the organic substance is an organic nitrile and dinitrile compound or derivative.

12. A method according to Claim 2, characterized in that the organic substance is an organic aldehyde compound or derivative.

13. A method according to Claim 2, characterized in that the organic substance is an organic acid compound or derivative.

14. A method according to Claim 2, characterized in that the organic substance is an organic amine compound or derivative.

15. A method according to Claim 1 , characterized by comprising the steps of:

- Placing the mixture, including metal powder, into a metal pipe whose one end is compressed by means of clamp

- Preferably applying vacuum into the pipe or filling inert gases like N2, Ar, C02, in order to remove the oxygen in the medium

- Closing the other end of the pipe

- Engaging the metal pipe, which is in capsule form whose two ends are closed and which is prepared and which comprises metal powder mixture, at least once and preferably 5-50 times back to back, through roll-milling machine, and bringing said metal pipe into an extended metal strip form.

- Preferably keeping the first step roll-milling process relatively shorter, and producing by means of roll-milling 5-50 times in open form after the obtained composite film is removed from the metal pipe,

- Filling back the nano metal powder and ceramic composite catalysers into a metal pipe, and bringing into film form, and keeping for consumption.

Description:
NOVEL PRODUCTION METHOD AND USE OF NEW NANO-METAL AND METAL- CERAMIC COMPOSITE CATALYSERS

TECHNICAL FIELD

The present invention relates to production of activated stabilized nano metal powders used in the synthesis of nano metal composites or in the synthesis of dyes which are metal complexes of the type Phtalocyanine, Naphtalocyanine, Porphyrazine, Porphyrine, sub- Phtalocyanine, sub-Naphtalocyanine, sub-Porphyrazine and sub-Porphyrine and in the synthesis of the other probable organic dyes, and the present invention relates to production of nano metal composites of these dyes by using mechanochemical roll-milling method. KNOWN STATE OF THE ART

In the known state of the art, it is known that metal powders are used in the production of some phtalocyanine metal complexes. However, it is not known that metal powders are used in the production of sub-phtalocyanine, sub-naphtalocyanine, sub-porphyrazine and sub- porphyrine type metal complexes.

At the same time, there is no method related to roll-milling of metal powders in open or closed encapsulated form and related to production of metal powder and composites activated by means of said method. There are probable problems such as spreading of the powders in the open medium, adhering of the powders to the roll-mill cylinders and oxidizing of the metal surfaces.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a method providing production of activated stabilized nano metal powders used in the synthesis of nano metal composites or in the synthesis of dyes which are metal complexes of the type Phtalocyanine, Naphtalocyanine, Porphyrazine, Porphyrine, sub-Phtalocyanine, sub-Naphtalocyanine, sub-Porphyrazine and sub-Porphyrine which have optic, electronic and medical properties with advanced technology, and in the synthesis of the other probable organic dyes, and providing production of nano metal composites of these dyes by using mechanochemical roll-milling method and providing production with high efficiency, stabilization, protection against oxidation, preservation for long time by means of encapsulation and providing repetitive roll-milling in an open manner and providing easy usage, for eliminating the above mentioned disadvantages and for bringing new advantages to the related technical field. The main object of the present invention is to provide a method providing production of nano metal composites at high efficiencies and providing preservation of nano metal composites for long duration.

Another object of the present invention is to provide a method providing repetitive roll-milling and providing ease-of-use.

In order to realize all of the abovementioned objects and the objects which are to be deducted from the detailed description below, the present invention is a method for providing roll-milling of a mixture, comprising at least one metal (M) powder, inside at least one metal pipe and for bringing the metal into nano particle dimensions.

In a preferred embodiment of the subject matter invention, metal reacts chemically during roll-milling of said nano-particles. In a preferred embodiment of the subject matter invention, said reaction takes place in the presence of at least one organic compound.

In a preferred embodiment of the subject matter invention, said reaction takes place in the presence of at least one organic compound, polymer or dye, and thereby metal is coated.

In another preferred embodiment of the subject matter invention, the metal is selected from Li, Na, K, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Se, Te. In another preferred embodiment of the subject matter invention, metal is in metal oxide form.

In another preferred embodiment of the subject matter invention, metal oxide is selected from Al 2 0 3 , ZnO, Ti0 2 , Si0 2 , MgO, B 2 0 3 , Zeolite and hydroxyapatite. In another preferred embodiment of the subject matter invention, the metal is in metal salt form. In another preferred embodiment of the subject matter invention, the metal salt is selected from F, CI, Br, I, CH3COO-, S0 4 2 -, C 2 0 4 2" , P0 4 3" , N0 3 " , OH " , C0 3 2" , HC0 3 " , H 2 P0 4 " , HP0 4 2" salts. In another preferred embodiment of the subject matter invention, the mixture comprises organic substance.

In another preferred embodiment of the subject matter invention, the organic substance is phthalonitrile or naphthalonitrile.

In another preferred embodiment of the subject matter invention, the organic substance is an organic nitrile and dinitrile compound or derivative.

In another preferred embodiment of the subject matter invention, the organic substance is an organic aldehyde compound or derivative.

In another preferred embodiment of the subject matter invention, the organic substance is an organic acid compound or derivative. In another preferred embodiment of the subject matter invention, the organic substance is an organic amine compound or derivative.

In another preferred embodiment of the subject matter invention, there are the process steps of:

Placing the mixture, including metal powder, into a metal pipe whose one end is compressed by means of clamp

Preferably applying vacuum into the pipe or filling inert gases like N 2 , Ar, C0 2 , in order to remove the oxygen in the medium

- Closing the other end of the pipe

Engaging the metal pipe, which is in capsule form whose two ends are closed and which is prepared and which comprises metal powder mixture, at least once and preferably 5-50 times back to back, through roll-milling machine, and bringing said metal pipe into an extended metal strip form.

- Preferably keeping the first step roll-milling process relatively shorter, and producing by means of roll-milling 5-50 times in open form after the obtained composite film is removed from the metal pipe, Filling back the nano metal powder and ceramic composite catalysers into a metal pipe, and bringing into film form, and keeping for consumption.

BRIEF DESCRIPTION OF THE FIGURES

In Figure 1 , the view of roll-milling of chemicals A and B in an encapsulated manner into a metal pipe inside M metal (a) and MO metal (b) oxide ceramic powder, processing in a mechanochemical manner, and grinding thereof into nano dimensions is given. In Figure 2, the view of roll-milling of the M1 and M2 (a), M1 and M30 (b), M1 , M2 and M30 (c), PN, M1 , M2 and M30 (d) and NN (naphthalonitrile), M1 , M2 and M30 (e) metal-ceramic chemicals, in an encapsulated manner into a pipe made of M4 metal, processing in a mechanochemical manner, grinding thereof into nano dimensions, and preparing composite electrode coatings is given.

In Figure 3, the view of roll-milling of the phthalonitrile (PN) (a) and naphthalonitrile (NN) (b) mixtures of M1 metal in the presence of M2X salt, in an encapsulated manner inside a pipe made of M4 metal, and grinding thereof into nano dimensions is given. In Figure 4, the view of roll-milling of the Zn Micro- particle powders by means of an organic binder (a) and in the presence of M2X salt of M1 metal (b), in an encapsulated manner inside a pipe made of M4 metal, and grinding thereof into nano dimensions is given.

In Figure 5, the view of roll-milling of metal or metal composite mixtures in an encapsulated manner inside a pipe made of M4 metal like Cu, Al, Ti, Ag, Au and Pt and in a multi-stepped manner as open film in the final step, and grinding thereof into nano dimensions is given.

In Figure 6, the SEM image of the Zn particles prior to roll-milling process is illustrated. In Figure 7, the TEM image of the nano zinc powders with dimensions of 50-100 nm obtained multi-step roll-milling with phthalonitrile PN addition is illustrated.

In Figure 8, (a) the SEM image of the Zn particles, which are deformed and whose SEM image is extended after the roll-milling process and (b) homogeneous nano powder distribution observed in powder surfaces are given. REFERENCE NUMBERS

I- Roll mill

2 - M1 Micro-particle

3 - M1 Nano-particle

4- Zn Micro-particle

5- Zn Nano-particle

6- Cu or Al Pipe

7- Metal or Metal Composite

8- Closed End

9- Adjustable Distance

10- Encapsulated Stabilized Nano Metal or Metal Composite

I I- Nano Metal thin film between Cu or Al surfaces

12- Partially Activated Nano Metal or Metal Composite Film Layer

13- Stepped Open Roll Milling Process

14- Activated Stabilized Nano Metal or Metal Composite Product

THE DETAILED DESCRIPTION OF THE INVENTION The present invention relates to production of activated stabilized nano metal powders used in the synthesis of organic dyes and various other chemicals or in the synthesis of nano metal composites and production of nano metal composites of these dyes by means of the specific mechanochemical roll-milling method. The subject matter mechanochemical roll-milling process is applied to mixtures preferably comprising a metal, and comprising or not comprising an organic, inorganic or ceramic type additive substance.

By means of the subject matter roll-milling method, the general activation process of the metal powders is described below:

The process of production of metal powders (Figure 6) like Zn, which are in macroscopic or microscopic dimensions, in nano dimensions in a mechanical or mechanochemical manner, is realized by means of multi-step roll-milling process (Figure 5). The roll-milling process essentially comprises optionally one or two steps depending on the application. In the first step, other additive substances are added to metal powder such that there is metal in the range of 0-90 %, preferably in the range of 0-60 %, and afterwards, pre-grinding and mixing process is applied inside a mortar or inside an electrical grinding device so as to obtain a homogeneous mixture. The prepared homogeneous mixture, which has a weight of approximately 0-250 grams, is placed inside a pipe made of M4 type metal (M4: Cu, Al, Zn, Ti, Sn, Fe, Ag, Au, Pt) approximately with diameter of 0-5 cm and length of 0-100 cm and whose one end is compressed and closed by means of a clamp and roll-milled, and the other end thereof is closed from a location which is close to the powder level. Before the end section is closed, preferably vacuum can be applied to the medium or inert gases like N 2 , Ar, and C0 2 may be filled in, in order to remove the oxygen in the medium. The metal pipe which is in capsule form whose two ends are closed and which is prepared and comprising metal powder mixture, is engaged as desired, depending on the diameter of the pipe, or preferably 5-50 times back to back, through a roll-milling machine which is similar to the machines used in metal sheet production and in jewelry processes, and thereby said metal pipe is brought into a metal strip form. During the roll-milling process, the distance, provided between the cylinders, is narrowed each time up to the desired level. Thanks to this encapsulated form, there is the possibility to easily keep and transfer the prepared active nano metal powder and store said active nano metal powder without air contact for long durations. Moreover, there is the possibility to partially remove the desired amount of sample by the user, without exposing the whole sample to air, thanks to the glove-box medium. Each edge is cut by means of metal sheet shearing, and the thin grinded film, formed in the middle, is removed. In the electron microscope examinations realized, it has been observed that the prepared sample is deformed and is brought into powder dimensions of nano and lower than micron. Preferably, the first roll-milling process is kept a little short, and the film, formed between the two plates, is removed as a whole so as to be slightly thicker. In the second roll-milling step which is preferably applied, the obtained metal film layer, which is short and relatively thick and which has dimension of 0-5 mm, is roll-milled approximately 0-10 times in an open manner, and it is brought into the form of long strips until it becomes thinner with a dimension of 0-0, 1 mm. The strips, which are in film form, are broken into small pieces, and they are stored in vacuum conditions or in inert medium, and they are used as catalyser and active component in chemical reactions.

As a result of the roll-milling process, metal can be separated from the roll-milling mixture by means of pluralities of methods. The metal mixture, which is to be used in the roll-milling process, comprises at least one metal. Said metal (M) can be in the form of metal salt (MX), metal oxide (MO) or a mixture of them. The metal foil, which is to be used in the roll-milling process, can be in the form of powder or particle. In the roll-milling process, metal or metal mixture and an organic or inorganic structured solid element, molecule or polymer can be used.

The M metal, used in the subject matter roll-milling process, is selected from Li, Na, K, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Se, Te.

The MO metal oxides used are selected from Al 2 0 3 , ZnO, Ti0 2 , Si0 2 , MgO, B 2 0 3 , Zeolite and hydroxyapatite.

The X in the MX metal salts used is selected from F,CI, Br, I, CH 3 COO-, S0 4 2 -, C 2 0 4 2" , P0 4 3" , NOV, OH " , C0 3 2" , HCOY, H 2 P0 4 " , HP0 4 2 \

In an application of the present invention, roll-milling process is directly applied to metal or double, triple metal mixtures without including organic or inorganic additive substance, and after this process, size reduction (a slight size reduction is observed, approximately the 100- 1000 nm range is possible), shape deformation and extension (the spherical powder micro- structure is completely extended and it turns into a layered micro-structure) occur and when the final open roll-milling process is applied, the crystals are expanded, fused and metalized on the surface.

In another application of the present invention, metal powder is grinded by means of roll- milling process in the presence of additive substances comprising various salts described above, organic dinitrile derivatives like phthalonitrile or the selected ceramics. In such an application, different micro particle structures are observed when compared with the grinding process without additive substances described above. In the electron microscope analyses made, it has been observed that the dimension distribution of the nano particles is smaller, and that pluralities of metal particles with dimension 30-100 nm can be obtained. Moreover, it has also been detected that the produced nano powders comprise surface deteriorations formed by breakages and moreover, it has been detected that they have more number of pores. Optionally and depending on the selected mixture, after multi-step roll-milling processes applied in an open and closed manner, it has been observed that the surfaces of the grinded metal powders are coated with an organic structured layer used as additive substance, and moreover, it has been observed that they form nano dimensioned core-shell structures. The structure of the produced composite powders is provided by using methods like SEM, TEM and XRD. In Figure 7, the SEM image of the Zn particles, which are deformed and whose SEM image is extended after the roll-milling process and homogeneous nano powder distribution observed in powder surfaces are given. In Figure 8, the TEM image of the nano zinc powders with dimensions of 50-100 nm obtained after multi-step roll-milling with phthalonitrile PN addition is illustrated. The open or closed roll-milling processes of metal powders can be easily applied in inert gas or vacuum medium by optionally forming a closed system. Again, in a similar manner, hot roll-milling processes can also be realized by heating the powder in capsule form particularly in mechanochemical roll-milling processes depending on the application to be realized. At the same time, the suggested roll-milling method is a chemical synthesis method. For instance, the substances A and B given in Figure 1 react with each other during mechanical grinding, and they can transform into a new substance whose properties are completely different. This application can be named as reactive roll-milling where mechanochemical transformations occur so as to be different from the above mentioned applications. By means of this method, various chemicals, dyes, medicines and cosmetic products can be synthesized and can be coated onto various solid support surfaces.

In another application of the present invention, the roll-milling process is used in preparation of composite electrode coatings.

In another application of the present invention, during the roll-milling process, a core-shell structure is obtained as a result of activation of metal and as a result of coating by the organic dye substance which is roll-milled together with metal. EXAMPLE 1

In Figure 1 , the roll-milling of chemicals A and B inside M metal and MO metal oxide ceramic powder in an encapsulated manner inside a metal pipe, and processing thereof in a mechanochemical manner, and grinding thereof to nano dimensions are presented.

In Figure 1 a, the process of grinding a mixture with two components comprising substances A and B inside a metal pipe together with metal M, and obtaining nano metal powder by means of roll-milling are illustrated. In Figure 1 b, the process of roll-milling a mixture comprising substances A and B, preferably only metal A or A-B metal mixture, more preferably M 2 X salt as metal A and component B, inside ceramic powder with type metal oxide or zeolite, hydroxyapatite and the production of A and B Nano metal powders are illustrated. A: Any solid element, molecule or polymer with organic or inorganic structure

B: Any solid element, molecule or polymer with organic or inorganic structure

M : Any metal

M 3 0: Metal oxides like AI203, ZnO, ΤΊ02, Si02, MgO, B203, hydroxyapatite and zeolites thereof

EXAMPLE 2 In Figure 2, the view of roll-milling of a) M1 and M2, b) M1 and M30, c) M1 , M2 and M30, d) PN, M1 , M2 and M30 and e) NN (naphthalonitrile), M1 , M2 and M30 metal-ceramic chemicals, in an encapsulated manner into a pipe made of M4 metal, processing in a mechanochemical manner, grinding thereof into nano dimensions, and preparing composite electrode coatings is given.

In Figure 2, obtaining Nano M1 by means roll-milling M1 metal with different components and in different shapes is illustrated.

Here; M or Μ·,: Li, Na, K, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Se, Te

M 2 : Li, Na, K, Ca, Mg, Ca , Ti, Cr, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, B, Al, Si, Sn, Se M 3 O: AI203, ZnO, ΤΊ02, Si02, MgO, B203, Zeolite and Hydroxyapatite

PN: Phthalonitrile and derivatives

NN: Naphthalonitrile and derivatives

M 4 : Cu, Al, Zn, Fe, Ti, Co, Ag, Au, Pt

X: F, CI, Br, I, CH 3 COO-, S0 4 2 -, C 2 0 4 2" , P0 4 3" , N0 3 " , OH " , C0 3 2" , HC0 3 " , H 2 P0 4 " , HP0 4 2" As a result of the process, M1 metal can be coated onto the M4 electrode surface as a thin film.

EXAMPLE 3 In Figure 3, the view of roll-milling of a) phthalonitrile (PN) and b) naphthalonitrile (NN) mixtures of M1 metal in the presence of M2X salt, in an encapsulated manner inside a pipe made of M4 metal, and grinding thereof into nano dimensions is given. In Figure 3, the dimensioning of M1 metal micro-particle (2) powders into the M2X salt by means of PN and NN into M1 nano particle (3) dimensions and the activation thereof are illustrated. Here,

X: F, CI, Br, I, CH 3 COO-, S0 4 2 -, C 2 0 4 2" , P0 4 3" , N0 3 " , OH " , C0 3 2" , HC0 3 " , H 2 P0 4 " , HP0 4 2" EXAMPLE 4 In Figure 4, the view of a) roll-milling of the Zn Micro-particle (4) powders into Zn nano- particle (5) by means of an organic binder like phthalonitrile (PN) and b) roll-milling of M1 micro-particle (2) metal in the presence of M2X salt, in an encapsulated manner inside a pipe made of M4 metal, and grinding thereof into M1 nano-particle (3) dimensions is given. In Figure 4, the grinding and roll-milling of Zn and M1 metal powders preferably by means of organic PN or inorganic M2X and the activation thereof are illustrated.

EXAMPLE 5 In Figure 5, the schematic view of open roll-milling (13) of metal or metal composite (7) mixtures in an encapsulated manner inside a pipe (6) made of Cu or Al preferably having a closed end (8), a pipe made of M4 metal like Cu, Al, Ti, Ag, Au and Pt and in a multi-stepped manner in the final step, and grinding thereof into nano dimensions is given. In Figure 5, the activation steps of the metals, which are applied by means of the two stepped roll-milling applied in closed form and in open form, are illustrated. In the first step, the metal or metal composite (7), provided in the Cu or Al pipe (6), is passed through the roll mill (1) having adjustable distance (9), and the encapsulated stabilized nano metal or metal composite (10) material is obtained. After roll mill (1), the Nano Metal thin film (1 1) existing between the Cu or Al surfaces is taken outwardly as Partially Activated Nano Metal or Metal Composite film Layer (12), and it is roll milled by means of stepped open roll milling (13), and the activated stabilized nano metal or metal composite product (14), which is the final product, is obtained. The application areas of the present invention are listed below:

1. As catalyser in any kind of organic and inorganic synthesis processes. 2. As initial substance in any kind of organic and inorganic synthesis processes.

3. In the production of solar battery OPV dyes and dyes used in LEDs.

4. In the production of composite nano metallic dyes.

5. In the production and storage of Core-Shell structured nano particles. 6. In the production of composite nano dyes with Metal, Metal-Dye, Dye-Ceramic, Metal- Ceramic and Metal-Dye-Ceramic structures.

7. In the processes of effectively coating composite nano dyes having Metal, Metal-Dye, Dye- Ceramic, Metal-Ceramic and Metal-Dye-Ceramic structures onto the conductive electrode surfaces like conductive Cu, Al, Ag, Ti and Pt at low temperatures

8. In any kind of chemical synthesis processes.