Title of Invention

PROCESS FOR MANUFACTURE OF NANOMETRIC, MONODISPERSE, AND STABLE METALLIC SILVER

Abstract The present invention relates to a procedure for preparation by a wet reduction method of nanometric particles of metallic silver, with diameter ranging from 1 to 100 nm and an average diameter of 20 to 40 nm, with monodispersion characteristics, stabilities exceeding 12 months and in a wide range of concentrations. The process comprises 4 stages: a) preparation of the reducing agent solution, taken from the tannins group and preferably tannic acid; b) preparation of a solution of soluble silver salts; c) reaction and, d) liquid-solid separation; the particle size is determined by the nature of the reducing agent and by the pH control of the currents. The final stage is designed for separating and concentrating the material after which the user can prepare the product for integration thereof in the desired medium. The particles obtained are redispersable in different media, such as water, alkidalic and phenolic resins, nitrocellulose, polyeurethane, vinylics, acrylics, alcohols, and in a wide range of organic and polymeric products such as high and low density polyethylene, Nylon, ABS and/or mixtures thereof.
Full Text FORM 2
THE PATENTS ACT 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10 and rule 13)



1. ' PROCESS FOR MANUFACTURE OF NANOMETRIC, MONODISPERSE, AND STABLE METALLIC SILVER AND PRODUCT OBTAINED THEREFROM '

2.

1. (A) SERVICIOS INDUSTRIALES PEÑOLES, S.A. DE C.V.
(B) A Company incorporated under the laws of Mexico
(C) Prolongacion Comonfort s/n Antigua Aduana Clonia Luis Echevarría C.P. 27300 Torreón, Coahuila, Mexico.


The following specification particularly describes the invention and the manner in which it is to be performed.

INVENTION FIELD

The present invention is related to the processes for the preparation of metallic nanoparticles, and specifically a process for the preparation of nanometric, monodisperse, stable metallic silver in different mediums.


ANTECEDENTS OF THE INVENTION.

It is well known that silver particles are used as bactericide and antiviral agents, and its function as a bactericide increases in a proportionally inverse relationship to the size of the particle, for that reason the nanoparticles are of special interest. This material also has applications as a catalytic of the hydrogenization of organic compounds, among others.

To avoid confusion in the use of certain terms in the present text, “nanoparticle” is generally used to refer to particles that have a diameter equal to or less than 100 nm; “monodisperse” is used to identify the particles with low variability in size and; “stability” is understood as the quality that the material has in not changing the size of the particles and the monodispersion without applying mechanical or chemical means during the storage period.

Basically, there exist two types of processes previously known for the fabrication of nanoparticles of metallic silver:
a) By plasma, where a bar of metallic silver is heated to vaporization, then the vaporized silver is cooled in a suitable atmosphere, obtaining a fine dust of metallic silver,(in an inert atmosphere) or a composite of silver associated to the nature of the atmosphere used.
b) By wet milling, where a silver ion solution is submitted to a process of reduction, in the presence of surfactants and stabilizers to control the size of the product.


Recently there have been reports of the effect of the presence of light in applications for the reduction of silver by wet milling (“Preparation of silver nanoparticles by photo-reduction for surface-enhances Raman scattering”; Huiying Jia, Jiangbo Zeng, Wei Song, Jing An, Bing Zhao; Thin Solid Films 496 (2006) 281 – 287. “Photochemical preparation of nanoparticles of Ag in aqueous solution and on the surface of mesoporous silica”; G. V. Krylova, A. M. Eremenko, N. P. Smirnova, S. Eustis; Theoretical and experimental chemistry (2005) 41(2) 105-110), where the addition of surfactants and stabilizers is not necessary, since the metallic silver particles form on the surface of a substrate; the reaction lasts 3 hours.

Xuelin (“Seedless, surfactantless photoreduction synthesis of silver nanoplates”; Xuelin Tian, Kai Chen, Gengyu Cao; Materials Letters 60 (2006) 828–830) reports of the use of a sodium citrate as the reducing agent to obtain silver nanoparticles in the presence of light.

In other articles, the precipitation of metallic silver nanoparticles is mentioned, where the reaction can last from 8 to 24 hours (CN1810422, Gao, 2006). In other publications to accelerate the reaction, the mixture is heated to temperatures close to 100°C (CN1686646, Liu, 2005; CN1669914, Luo, 2005).

It is clear that in the case of the process of wet milling, a significant problem exists in the selection of additives since they should be compatible between the surfactant used in the reaction and the application for which the nanoparticles are destined, or on the contrary, submit the product to a process to eliminate the surfactant; furthermore, the concentration of the additive in the reaction mixture needs to be controlled to influence the size of the silver nanoparticles; on the other hand, it is important to point out that the reaction times are relatively long, such that there is a wide variety in the distribution of particle size.

OBJECTIVES OF THE INVENTION

In light of the problems found in the previous articles, it is an objective of the present invention to provide a new process for the preparation of metallic silver particles.

Another objective of the present invention is to provide a wet milling process that simplifies the control of the nanoparticle sizes obtained.

Another objective of the present invention is the production of monodisperse metallic silver nanoparticles.

Still another objective of the present invention is the production of metallic silver nanoparticles with an average diameter of between 1 and 100 nm.

Another objective of the present invention is the production of metallic silver nanoparticles with an average diameter of between 5 and 60 nm.

Another objective of the present invention is the production of metallic silver nanoparticles with stability superior to twelve months.

Another objective of the present invention is to provide a product of silver nanoparticles that disperse easily in a variety of applications.

Another objective of the present invention is to provide a process by means of the reduction of the original humidity (wet milling) for the production of metallic silver nanoparticles in large concentrations.


A BRIEF DESCRIPTION OF THE FIGURES

To understand the material of the invention better, the description is accompanied by a series of figures that are illustrative of the reach of the same. They will be described as follows:

Figure 1 is a diagram including blocks representing the process to obtain the metallic silver nanoparticles of the invention.

Figure 2 is a graph that shows the distribution of the sizes of particles of nanometric silver in the product by the process of the invention.

Figure 3 is a graph that shows the distribution of the particle sizes of the nanometric silver in another product by the process of the invention.

Figure 4 is a micrograph of nanometric and monodisperse metallic silver in a product prepared for the procedure described in the present invention.

Figure 5 is a micrograph of the nanometric and monodisperse metallic silver, in another product prepared for the procedure described in the present invention.


A BRIEF DESCRIPTION OF THE INVENTION.
The present invention is related with the process of wet milling for the preparation of nanometric particles of metallic silver, and the product obtained through the same. The particles have a diameter in a range of between 1 and 100 nm, the average diameter between 20 and 40 nm, and the following characteristics: being monodisperse, having a stability greater than 12 months and having a large range of concentrations.

The process of the present invention requires as a base material, a solution of soluble silver salts, such as sulfates, nitrates and others, having an adjusted pH in the alkaline range by the controlled addition of alkalis such as, hydroxide of sodium, potassium, ammonium, and ammonia. Tannins are used as the reducing agents, including in this category tannic acid.

An important aspect of the invention is related with the adequate control of the pH of the solutions before, during and after the reaction since it has a relevant affect on the size of the particle and its variability.

The main difference between the proposed process in the present invention and those in the state of the technique is the use of tannins and preferably tannic acid as the reduction agent, that besides controlling the size of the particle to values less than 100 nm, it has the additional advantage of fulfilling the function of the surfactants and the stabilizers in the known processes, thus making their addition unnecessary and in this way, simplifying the production process, at the same time that it impedes the agglomeration of the nanoparticles produced during the reaction and the reagglomeration after the stages of purification.

The process has 4 stages:
a) prepare an aqueous solution of the reducing agent to a concentration from 0.01% to 20% in weight, the concentration and the quantity of the solution directly influences the efficiency of the reaction and the size of the particle obtained;
b) prepare an aqueous solution of a silver salt with a concentration of from 0.01% to 20% in weight;
c) mix the reducing solution and the silver solution in a reactor; during the reaction, the pH is controlled with ammonium hydroxide in values between 10.5 and 11.5; the duration can be up to 1.0 hour, but in approximately 15 minutes a conversion of greater than 95% is reached;
d) remove the nanoparticles of formulated metallic silver from the mother liquor by any means of separation of solids and liquids, such as decantation, centrifugation, filtration, etc.

It has been found that the reaction is accelerated with the presence of day light.

As it has been previously mentioned, the use of tannins or tannic acid as the reducing agent eliminates the need to use another type of additive to control the size of the nanoparticles that are obtained, nonetheless, there exists variations in the process described above that in addition to the use of tannins, allows for the control of the range of the average sizes, as is described in continuation.

In one model of the invention, the size of the nanoparticles is controlled through the adjustment of the pH of the silver salt solution in the alkaline range until a value of 11.5 by the addition of the ammonium hydroxide. It is observed that when the pH of this solution is not controlled before the reaction, the nanoparticles that result from the reaction will have an average particle size around 40 to 50 nm and the formation of silver oxide will be detected. The silver oxide reduces the yield of the process.

In another model of the invention, the pH of the reducing solution is controlled in the alkaline range until a value of 11.5 through the addition of the ammonium hydroxide.

The modification of the pH in one or both of the solutions described in the previous models, before their mixture, has noticeable effects on the size of the nanoparticles in the final product.

The separation of the phases to obtain the nanoparticles free from the mother liquor is made easier if the “zeta potential” (that represents the electric charge on the surface of the particles and their integration with other particles) is changed, be it by the addition of flocculants or by the acidification of the solution until the flocculation of the nanoparticles.

The product obtained through the process or any other of the models is a wet paste, that has particles that are redispersible into different mediums such as water, alcohols, alkydalic and phenolic resins, nitrocellulose, polyurethane, vinylics, acrylics and in a wide variety of organic materials and polymers such as high and low density polyethylene, Nylon, ABS and or mixtures of the same.

DETAILED DESCRIPTION OF THE INVENTION.
The present invention is related with a process of wet milling for the preparation of nanometric particles of metallic silver through the reaction of two solutions, one of which is an aqueous solution of some salt soluble in silver, selected from a group that includes sulfates and nitrates, and a reducing solution, from a reducing agent selected from the group of tannins, preferably being tannic acid.
The main advantage of using tannins and tannic acid in particular as the reduction agent in the aqueous solution, lies in the fact that besides controlling the particle size to values smaller than 100 nm, it replaces the surfactants and stabilizers in the known processes, simplifying the process, at the same time impeding the agglomeration of the nanoparticles produced during the reaction and their reagglomeration after the stages of purification.

It is necessary to maintain adequate control of the pH of the solutions before, during and after the reaction, to make sure the production of the nanoparticles have an average size within the defined range, and with little variation in their dimensions (monodisperse), as can be seen in Table 1 which includes the typical results with the different possibilities of the invention.

Table 1. Effect of the pH on the reducing solution and the silver salt solution on the average size of the nanoparticles.

Reducing solution
Solution of
Silver salt With pH adjustment Without pH adjustment
With pH adjustment 10-20 nm 20-30 nm
Without pH adjustment 40-50 nm
Formation of silver oxide 40-50 nm
Formation of silver oxide

As is evident from the data in Table 1, the effect of not adjusting the pH of the silver salt solution to the values that will be signaled later on, results in a product with average particle sizes relatively larger and in the formation of silver oxide, that on one hand reduces the yield of the process and on the other hand results in a “contaminated” product that will have a lower efficiency in some of the final applications.

Upon continuation the details of the procedure of the invention itself that is illustrated in Figure 1 will be presented, where the operations and the paths described are indicated by the number in parenthesis.

Stage 1. Preparation of the reduction solution (100)
Dissolve a reductant (5), selected from the group that includes tannins and preferably, being tannic acid, in water (10) free from halogens, to form an aqueous solution (35) with a concentration from 0.01% to 20% in weight.
In an alternative model, and conform to that established in Table 1, adjust the pH in the reducing solution into the alkaline range until a maximum value of 11.5 through the addition of an hydroxide (25) selected from a group that includes hydroxides of sodium, potassium, ammonium, and ammonia, preferably being ammonium hydroxide.

Stage 2. Preparation of the silver solution (200)
Dissolve the silver salt (15), selected from a group that includes sulfates and nitrates, and preferably being silver nitrate, in water (20) free of halogens, to form an aqueous solution (40) with a concentration from 0.01% to 20% of weight.
In an alternative model, and according to that established in Table 1, adjust the pH in the silver salt solution into alkaline range until a maximum value of 11.5 through the addition of an hydroxide (30) selected from a group that includes hydroxides of sodium, potassium, ammonium, and ammonia, preferably being ammonium hydroxide, due to its effect to be able to slow the ageing of the solution.
The aqueous silver solution preferably should be prepared immediately before realizing the reaction and a maximum of 15 minutes before its usage.

Stage 3. Reaction and production of the metallic silver nanoparticles (300)
In a reactor, mix the reducing solution (35) and the silver salt solution (40) assuring an efficient mixture, under the conditions of room temperature and pressure, for a period of at least 15 minutes, which is the time sufficient enough to reach a conversion greater than 95%; the laboratory tests show the presence of light has the effect of increasing the speed of the reaction, for that reason it is recommended to use a reactor with walls that allow for the passage of light.

Immediately after adding the reducing solution (35) and the silver salt solution (40), adjust the pH of the mixture by adding ammonium hydroxide (50) until the value is between 10.5 and 11.5, preferably 10.5.

The result of the reaction is a suspension (45) of monodisperse metallic silver nanoparticles.

Stage 4. Separation from the mother liquor (400)
For the separation of the mother liquor (55) from the suspension of the silver nanoparticles (45) any method of solid-liquid separation can be used, such as sedimentation, filtration, or centrifugation. To ease the separation of stages, flocculants or acids (65) that modify the zeta potential can be used. Preferably, use an acid within the same functional group as that of the silver salt used.
The product (60) thus obtained is a wet paste of nanometric, stable, easily dispersible metallic silver, with low variability in the distribution of particle size (monodisperse) and with an average particle size in the range of 1 to 100 nm, depending on the means of preparation related with the adjustment of the pH before the reaction.
The product containing the silver nanoparticles (60), can be submitted to other washing processes with water or other organic solvents, monomers or resins, according to what is needed for the application of the final user.
As has been previously mentioned, the product obtained by the described process, including the preferred models is a wet paste in which the particles are redispersible in different mediums, such as water, alcohol, alkydalic and phenolic resins, nitrocellulose, polyurethane, vinylics, acrylics and in a wide variety of organic materials and polymers such as high and low density polyethylene, Nylon, ABS and or mixtures of the same.

Figure 2 is a graph of the distribution of the size of the particle of the metallic silver in the paste obtained by the invention process, where the distribution of particle size can be observed in which the average (D50) is 47.0 nm and where 90% of the particles have a size (D10) greater than 41.5 nm and where 90% of the particles have a particle size (D90) less than 56.0 nm. The measurements have been completed by the diffraction of laser rays, by equipment marked Coulter LS230.

Figure 3 is a graph of the distribution of the particle sizes of nanometric silver obtained by the invention process where it shows the following distribution of particle sizes: D10, 4.7 nm; D50, 21.0 nm; D90, 40.7 nm. The measurements were taken by attenuation of ultrasound, by the equipment marked AcoustoSizer II.

Figure 4 is a micrograph of the nanometric and monodisperse metallic silver product, with particle sizes between 10 and 20 nm, prepared by the procedure of the present invention.

Figure 5 is a micrograph of the nanometric and monodisperse metallic silver product with particle sizes between 5 and 20 nm, prepared by the procedure of the present invention, with which it is proved the range of particle sizes are between 1 and 100 nm.

The previous description for the process of the present invention reflects the stages necessary to be sure that the product obtained reaches the following qualities of the metallic silver nanoparticles: homogeny, stability, monodispersion, and others that have already been described, and furthermore including the preferred models; nonetheless, said description and the accompanying figures should be considered illustrative of the process and the product, and not limiting to the same. For a person with knowledge of the material, it will be evident that variations can be introduced in order to carry out the process of the invention, but said variations cannot be considered outside the reach of the present invention, which will be further described in the following claims.






We Claim:-
Once the invention has been described, that which is considered new and thus claimed as property is:

1 A process by wet milling to produce monodisperse and stable nanoparticles of metallic silver, made up of the following stages:
a) to prepare a aqueous solution of silver salts, containing from 0.01% to 20% in weight of a silver soluble salt
b) to prepare a aqueous solution of the reducing agent, that contains from 0.01% to 20% in weight of a composite from the group of tannins
c) to mix the aqueous solutions to produce their reaction, and
d) to separate the mother liquor from the silver nanoparticles,
the process is characterized by:
i) the adjustment of the pH of the aqueous silver salt and reducing solutions to values between 10.5 and 11.5,
ii) the reaction is realized by mixing the solutions and controlling the pH within the values of 10.5 and 11.5.



2 The process to produce nanometric metallic silver according to claim 1 is additionally characterized because the pH of the reducing solution is adjusted in the alkaline range preferable to a value up until 11.5.
3 The process to produce nanometric metallic silver according to claim 2 is characterized because to modify the pH in the reducing solution, the hydroxide used is selected from the group that includes sodium, potassium, ammonium, and ammonia hydroxide.

4 The process to produce nanometric metallic silver according to claim 3 is characterized because to modify the pH of the reducing solution, ammonium hydroxide is used.

5 The process to produce nanometric metallic silver according to claim 1 and 2 is characterized because, when the pH of the reducing solution is adjusted, the product that is obtained from the process has average particle sizes around 10 to 20 nm when the silver salt solution also has an adjusted pH value of alkaline of up until 11.5.

6 The process to produce nanometric metallic silver according to claim 1 and 2 is characterized because when the pH of the reducing solution is not adjusted, the product obtained from the process has average particle sizes of between 20 and 30 nm when the solution of silver salts also has the pH adjusted to alkaline values of up to 11.5.

7 The process to produce nanometric metallic silver according to claim 8 is characterized because, the pH of the silver salt solution is adjusted in the alkaline range preferably to a value of 11.5.

8 The process to produce nanometric metallic silver according to claim 7 is characterized because a hydroxide selected from the group that includes hydroxides of sodium, potassium, ammonium and ammonia is used to modify the pH of the silver salt solution.

10 The process to produce nanometric metallic silver according to claim 1, and 7 is characterized because, when the pH of the silver salt solution is not adjusted, the product that is obtained in the process has average particle sizes around 40 to 50 nm and forms silver oxide, that diminishes the quality of the product.

11 The process to produce nanometric metallic silver according to claim 1 is characterized because the silver salt solution is prepared no more than 15 minutes before the reaction with the reducing solution to avoid its aging.

12 The process to produce nanometric metallic silver according to claim 1 is characterized because the mixture of the reaction of the reducing solution and the silver salt solution takes place in the presence of light, preferably day light.

13 The process to produce nanometric metallic silver according to claim 1 is characterized because the mixing of the reaction is preferably less than 30 minutes.

14 The process to produce nanometric metallic silver according to claim 13 is characterized because the mixing of the reaction is for at least 15 minutes.

15 The process to produce nanometric metallic silver according to claim 14 is characterized because the progress of the reaction after 15 minutes is at least 95%.

16 A paste of nanoparticles of metallic silver obtained from the process according to claim 1, is characterized because the particles present a distribution of sizes in a monodisperse order.

17 A paste of nanoparticles of metallic silver obtained from the process according to claim 1, is characterized because the particle size is in the range between 1 and 100 nm.

18 A paste of nanoparticles of metallic silver obtained from the process according to claim 1, is characterized because the average particle size (D50) is preferably between 20 and 40 nm.

19 A paste of nanoparticles of metallic silver obtained from the process according to claim 1, is characterized because the metallic silver nanoparticles, can be easily redistributed into water, alcohols, alkydalic and phenolic resins, nitrocellulose, polyurethane, vinyl and acrylic resins, organic materials and polymers such as high and low density polyethylene, Nylon, ABS and or mixtures of the same and other solvents.

20 A paste of nanoparticles of metallic silver obtained from the process according to claim 1, is characterized because it is stable for periods of storage longer than 12 months without requiring mechanical labor for the redistribution of particles for the end user.

21. A process for manufacture of nanometric, monodisperse, and stable metallic silver and product obtained therefrom as herein described with forgoing description & drawings.

Dated this 13th day of June 2009.

Documents:

1123-MUMNP-2009-ASSIGNMENT(28-12-2011).pdf

1123-MUMNP-2009-CANADA DOCUMENT(27-9-2012).pdf

1123-MUMNP-2009-CLAIMS(22-6-2009).pdf

1123-MUMNP-2009-CLAIMS(AMENDED)-(1-11-2013).pdf

1123-MUMNP-2009-CLAIMS(AMENDED)-(27-9-2012).pdf

1123-MUMNP-2009-CLAIMS(MARKED COPY)-(1-11-2013).pdf

1123-MUMNP-2009-CLAIMS(MARKED COPY)-(22-6-2009).pdf

1123-MUMNP-2009-CLAIMS(MARKED COPY)-(27-9-2012).pdf

1123-MUMNP-2009-CN DOCUMENT(27-9-2012).pdf

1123-MUMNP-2009-CORRESPONDENCE(2-9-2009).pdf

1123-MUMNP-2009-CORRESPONDENCE(20-8-2009).pdf

1123-MUMNP-2009-CORRESPONDENCE(22-6-2009).pdf

1123-MUMNP-2009-CORRESPONDENCE(4-10-2010).pdf

1123-MUMNP-2009-CORRESPONDENCE(6-6-2011).pdf

1123-MUMNP-2009-CORRESPONDENCE(7-8-2013).pdf

1123-MUMNP-2009-DECLARATION(2-9-2009).pdf

1123-MUMNP-2009-ENGLISH TRANSLATION(28-12-2011).pdf

1123-MUMNP-2009-EP DOCUMENT(27-9-2012).pdf

1123-MUMNP-2009-FORM 1(20-8-2009).pdf

1123-MUMNP-2009-FORM 1(4-10-2010).pdf

1123-mumnp-2009-form 13(4-10-2010).pdf

1123-MUMNP-2009-FORM 18(22-6-2009).pdf

1123-MUMNP-2009-FORM 2(TITLE PAGE)-(4-10-2010).pdf

1123-MUMNP-2009-FORM 26(20-8-2009).pdf

1123-MUMNP-2009-FORM 26(4-10-2010).pdf

1123-MUMNP-2009-FORM 3(1-11-2013).pdf

1123-MUMNP-2009-FORM 3(20-8-2009).pdf

1123-MUMNP-2009-FORM 3(27-9-2012).pdf

1123-MUMNP-2009-FORM 5(20-8-2009).pdf

1123-mumnp-2009-form 6(4-10-2010).pdf

1123-MUMNP-2009-FORM PCT-IPEA-409(27-9-2012).pdf

1123-MUMNP-2009-OTHER DOCUMENT(1-11-2013).pdf

1123-MUMNP-2009-OTHER DOCUMENT(4-10-2010).pdf

1123-MUMNP-2009-PETITION UNDER RULE-137(1-11-2013).pdf

1123-MUMNP-2009-REPLY TO EXAMINATION REPORT(1-11-2013).pdf

1123-MUMNP-2009-REPLY TO EXAMINATION REPORT(27-9-2012).pdf

1123-MUMNP-2009-REPLY TO EXAMINATION REPORT(28-12-2011).pdf

1123-MUMNP-2009-RU DOCUMENT(27-9-2012).pdf

Drawings.doc

Form-1.doc

Form-3.doc

Form-5.doc

Priority Document.pdf


Patent Number 260038
Indian Patent Application Number 1123/MUMNP/2009
PG Journal Number 14/2014
Publication Date 04-Apr-2014
Grant Date 31-Mar-2014
Date of Filing 13-Jun-2009
Name of Patentee SERVICIOS ADMINISTRATIVOS PENOLES S.A. DE C.V.
Applicant Address CALZADA MANUEL GOMEZ MORIN NO.444, COL. TORREON RESIDENCIAL, TORREON COAHUILA.C.P.27268, MEXICO
Inventors:
# Inventor's Name Inventor's Address
1 MARTÍNEZ MARTÍNEZ Jesús Manuel Jardines del Escorial No. 7624 Col. Fracc. Jardines de Andalucia C.P. 67193 Guadalupe Nuevo León Mexico
2 BENAVIDES PÉREZ Ricardo Av. del Acueducto No. 6414 Col. Ciudad Satélite C.P. 64960 Monterrey Nuevo León Mexico
3 BOCANEGRA ROJAS José Gertrudis Lago Maracaibo 6923 Col. Lagos del Bosque C.P. 64890 Monterrey Nuevo León Mexico
4 RUIZ Facundo Cordillera Himalaya 894 Col. Lomas 4to. Sector C.P. 78216 San Luis Potosí San Luis Potosí Mexico
5 VÁZQUEZ DURÁN Alma Guadalupe Tabacos 174 Col Frac. Tecnológico C.P. 78146 San Luis Potosí San Luis Potosí Mexico
6 MARTÍNEZ CASTAÑON Gabriel Alejandro Lago Zumpango 307 Col. Frac. Constitución C.P. 78300 San Luis Potosí S.L.P. Mexico
PCT International Classification Number B22F9/24
PCT International Application Number PCT/MX2007/000047
PCT International Filing date 2007-04-03
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NL/a/2006/000107 2006-12-20 Mexico