Patent Grant
7829493
The present invention refers generally to the nanoparticles field, particularly to the field of metallic nanoparticles, and more especially to the area of nanoparticles homogeneously dispersed over supports.
Nanomaterials or nanostructured materials are heterogeneous systems constituted by particles which size ranges between 1 and 100 mm (10−9 to 10−7 m). These systems have physical properties that can be very different from those found in equivalent systems which size is that of a micrometric grain. Amongst the most notable physical properties that appear at the nanometric scale are the quantization phenomena (charge, electronic levels . . . ); the confining phenomena (electronic, dielectric [Flytzanis, C., Hache, F., Kelin, M. C., Ricard, D., and Roussignol, Ph., “Nonlinear Optics in Composite Materials”, Prog. Optics, 29, 322 (1991)]; the presence of monodomains (crystalline, ferromagnetic [B. D. Cullity. “Introduction to Magnetic Materials”, Addison-Wesley, California, 1972, 117-119 and 309-311], ferroelectrical); giant magnetorresistance effect [J. I. Gittleman, Y. Goldstein, and S. Bozowski, Phys. Rev. B 5 3609 (1972)]; Hall-Petch effect or suppression of dislocation pileups, [H. Gleiter, Progress in Mater. Sci., 33, 223 (1989); V. G. Gryzanov and L. I. Trusov, Progress Mater. Sci., 37 289 (1993)], etc.
Currently there is a great effort in global R+D focused both on the production and the characterization of these nanoparticled materials with the further objective to manufacture new products and devices.
Particularly, the metallic nanoparticles are one of the most studied nanomaterials since they display physical properties that are unique to insulators and conductors or a mixture of both [H. Gleiter, Progress in Mater. Sci., 33, 223 (1989), V. G. Gryaznov and L. I Trusov, Progress Mater. Sci., 37 289 (1993)]. These materials are currently being used in colloidal and catalysis chemical processes. On the other hand the expectation is that in the near future metallic nanomaterials may be used to manufacture “opto” and/or electronic devices.
Currently, the synthesis of nanoparticles is achieved by several methods, such as: mechanical activation [Eric Gaffet, Fréderic Bernad, Jean-Claude Niepce, Fréderic Charlot, Chirstophe Gras, Gérard Le Caér, Jean-Louis Guichard, Pierre Delcroix, Alain Mocellin and Olivier Tillement. “Some Recent Developments in Mechanical Activation and Mechanosynthesis”, Journal of Material Chemistry, 9, 305-314 (1998)]; wet synthesis methods (hydrothermal and thermal decomposition of the precursor material), sol-gel [D. G. Morris, “Mechanical Behavior of Nanostructured Materials”, Vol. 2 of Materials Science Foundations, Trans Tech Publications Ltd, (1998)]; synthesis during the gaseous phase, electrochemical methods [Ebrahimi, F. Bourne, G. R. Kelly, M. S. and Matthews, T. E., Nanostruct. Mater., 1999, 11 343]; chemical epitaxial growth [Veprek, S. J., Vac. Sci. Technol. A, 1999 17 2401]; (CVD (Chemical Vapor Deposition), or by molecular beams [Philip Moriarty, Nanostructured Materials, Reports on Progress in Physics, 64], 297-381 (2001)] (MBE, Molecular Beam Epitaxy), ion sputtering procedures [J. Musil, I. Leipner, M. Kolega, Surf. Coat. Tech, 115, 32-37, (1999)], etc.
Depending on the type of material obtained these techniques are grouped as epitaxial techniques (MBE, CVD and ablation) and massive techniques (all others). However, one of the main problems encountered when preparing these materials is their tendency to cluster, causing the disappearance of the properties inherent to the nanometric dimensions. In the only instances in which a good control of the microstructure has been achieved (such as in MBE), the quantity of material prepared is very small, which considerably increases the possible manufacturing costs and prevents a viable industrial exploitation. This is the reason that has prompted several groups to dedicate considerable efforts to obtain perfectly dispersed nanocrystals in oxidic matrixes [K. Niihara, “New Design Concept of Structural Ceramics-Ceramic Nanocomposites”, J. Ceram. Soc. Jpn. 99 (1991) 974; S. T. Oh, M. Sando and K, Niihara, “Mechanical and magnetic properties of Ni—Co dispersed Al2O3 nanocomposites”, J. Mater. Sci. 36 (2001) 1817; T. Sekino and K. Niihara, “Microstructural characteristics and mechanical properties for Al2O3/metal nanocomposites”, Nanostructural Materials, Vol. 6 (1995) 663; T. Sekino, T. Nakajima, S. Ueda and K. Niihara, “Reduction and Sintering of a Nickel-Dispersed-Alumina Composite and its Properties”, J. Am. Ceram. Soc., 80, 5 (1997) 1139; M. Nawa, T. Sekino and K. Niihara, “Fabrication and Mechanical Properties of Al2O3/Mo Nancomposites”, J. Mater. Sci., 29 (1994) 3183; S. T. Oh, T. Sekino and K. Niihara “Fabrication and Mechanical Properties of 5% vol Copper Dispersed Alumina Nanocomposite”, J. Eur. Ceram. Soc., 18 (1998) 31; R. Z. Chen and W. H. TUan, “Pressureless Sintering of Al2O3/Ni Nanocomposites”, J. Eur. Ceram. Soc., 19 (1999) 463; K. Niihara, T. Sekino, Y. H. Choa, T. Kusunose, Y. Hayashi, K. Akamatsu, N. Bamba, T. Hirano and S. Ueda “Nanocomposite Structural Ceramics with Advanced Properties”, Proc. 4th Japan International SAMPE (1995); K. Niihara, T. Sekino, Y. H. Choa, T. Kusunose, Y. Hayashi, K. Akamatsu, N. Bamba, T. Hirano and S. Ueda, “Nanocomposite Structural Ceramics with Advanced Properties”, Proc. 4th Japan International SAMPE. (1995)]. It is in this field where the development of a simple, efficacious and cheap method to prepare metallic nanoparticles is of considerable interest, from the industrial perspective, since it would allow the manufacture of new devices based in the properties of the nanomaterials at very competitive prices.
The objective of the present invention is to overcome most of the obstacles present in the current art by implementing a simple, economic, and viable procedure to prepare nanoparticles at the industrial scale by homogenously dispersing a metallic compound in contact with a support, in which the support is at least a clay with a silicate network selected from the pseudolaminar phyllosilicate clays. According to the present invention, the clay may be a sepiolite clay, including the natural mineral sepiolites and the treated sepiolites such as rheologic grade sepiolite (as those marketed by TOLSA S. A:, Madrid, Spain under the PANGEL brand and obtained from natural sepiolite by special micronization processes that substantially avoid fiber breakage and described, for instance, in the patent applications EP-A-0170299 and EP-A-0454222), mineral or treated atapulgite, such as rheologic grade atapulgite (like the one found in the ATTAGEL product range manufactured and commercialized by Engelhard Corporation in the United States, and the MIN-U-GEL product range offered by the Floridin Company, or those obtained by treating atapulgite with the process described in patent EP-A-0170299). Conveniently, the support is a powder which particle size is smaller than 44 μm and preferably smaller than 5 μm.
Sepiolite and atapulgite or palygorskite belong to the pseudolaminar phyllosilicate clays, also known as palygorskite-sepiolite group, which structure determines a microfibrous or acicular morphology.
Hence, sepiolite is a hydrated magnesic silicate, although there are also aluminic sepiolites (in which 19% of the octahedral positions are occupied by aluminum ions), ferric sepiolites (called xylotile), nickelferrous sepiolites (falcondoite) and sodic sepiolites (loughlinite). Palygorskite, or atapulgite, is a hydrated aluminum magnesium silicate with a structure similar to that of sepiolite. According to Brauner and Preisinger, sepiolite is structurally formed by talcum type strands composed by two layers of silicon tetrahedrons joined by oxygen atoms to a central layer of magnesium octahedrons. These talcum-type strands are arranged in such a manner that the silicon tetrahedral layer is continuous, but the silicon tetrahedrons are inverted at intervals of six units. This structure determines the acicular morphology of the sepiolite particles, elongated along the axis c, and the presence of channels, called zeolitic channels, oriented in the direction of the c axis of the acicular particles and measuring 3.7 Å×10.6 Å, where water and other liquids can penetrate. As a result of this structure, sepiolite has a very high specific surface area that is due not only to the high external surface, but also to the internal surface originated by the zeolitic channels. The theoretical total specific surface of sepiolite, calculated in base to structural models, is of 900 m2/g., of which 400 m2/g belong to the external area and 500 m2/g to the internal area. However, not all of the sepiolite surface is equally accessible to all molecules. The accessible surface of sepiolite depends of the adsorbate used, of its size and of its polarity, which determines the accessibility of the adsorbate molecule to the clay's micropores and the zeolitic channels. The accessible BET surface to N2 is more than 300 m2/g, one of the highest surfaces found in a natural compound.
Atapulgite has a similar structure, although in this case the inversion of the silicon tetrahedrons occurs every other four tetrahedrons, instead of every other six as in the case of sepiolite. As a result, the atapulgite's zeolitic channels have a section of 3.7 Å×6.4 Å, that is, smaller than those of the sepiolite's channels, and therefore, atapulgite's specific surface, at approximately 150 m2/g, although high, is also smaller than that of sepiolite's.
The microfibrous particles of sepiolite and atapulgite are, in their natural state, arranged in clusters that form great bundles of acicular particles randomly arrayed in a structure analogous to that of a haystack. The structure thus formed is very porous and has a high volume of mesopores and macropores. By using special milling and micronization techniques, such as those described in patent EP-A-0170299, it is possible to de-agglomerate these microfiber beams into individual microfibrous particles while maintaining the high “aspect ratio”, that is the length/diameter ratio. These procedures allow the adsorbed molecules easier access to the external surface, therefore increasing the surface accessible for adsorbtion. Treating sepiolite and atapulgite thermally in order to eliminate the water adsorbed on the surface, and particularly, the water linked by hydrogen bridges to the water molecules of crystallization that complete the coordination of the magnesium atoms—in the case of the sepiolite- or the magnesium and aluminum atoms—in the atapulgite's case-located at the edge of the structure, both in the internal zeolitic channels as in the open channels located at the edge of the structure, serves to also increase the adsorption capacity of these clays.
Obtaining metallic nanoparticles over the clay's surface may be done by using any of the paligorskite-sepiolite clays, for instance, sepiolite, atapulgite and their combinations, and sepiolite and/or atapulgite mineral provided they are present in a concentration in which the sum exceeds 50%, and preferably if it is 85%, since the contamination by other minerals such as calcite, dolomite, feldspar, mica, quartz or smectite, besides diluting the clay over which the nanoparticles can form, can also affect the final properties of the product, as well as the development of the process itself, both during the precipitation of salts, hydroxides or oxides, and during the thermal treatment applied for the reduction of the metal.
Also, the metallic compound is, at the least, a precursor selected from the salts, hydroxides and oxides of the metallic elements, and the metallic element is selected from metallic elements susceptible to reduction at temperatures that are below the temperature at which the clay silicate network collapses. Some adequate metallic elements are Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au and their alloys or combinations thereof. These metallic elements are present in precursors such as hydrosoluble salts (chlorides, nitrates and sulphates).
The procedure described in the present invention also includes a deposition stage in which the precursor is deposited over the support, and when said precursor has been selected from salts and hydroxides, the procedure also entails a thermal decomposition stage in controlled atmosphere in which the precursor is decomposed into the oxide of the metallic element of choice. Later, a reduction stage is carried out in which the oxide of the metallic element is subject to a complete reduction process under controlled partial oxygen pressure (p02) and temperature conditions to finally obtain metallic nanoparticles deposited over the support.
The procedure is done at temperatures below that at which the silicate network of the clay would be destroyed, and preferably, at temperatures below 850° C., since at higher temperatures the sepiolite and the atapulgite suffer profound structural transformations that lead to the destruction of the silicate network as well as the potential appearance of other stages, such as clinosteatite, in the case of the vitreous phase of sepiolite.
One of the embodiments of the deposition stage entails dissolving the precursor in water to obtain a dilution of the precursor, disperse the support in said precursor dilution to obtain a precursor/support dispersion, and dry the precursor/support dispersion to obtain dry precursor/support particles. To enhance the degree of dispersion of the clay the preferred method is to apply mechanical stirring with high powered shear blades.
Preferably, and depending on the desired results, the precursor dilution is adjusted to a precursor concentration of 5 to 15%, the support diluted in water or in precursor dilution is adjusted to a 5 to 15% concentration. In addition, and conveniently, the support/precursor dispersion may be adjusted to a metallic element/support ratio in a range from 0.1:100 to 100:100 as a function of the desired density of the nanoparticles to be obtained on the surface of the support, and more preferably within a 5:100 to 50:100 range by weight.
When the aim is to precipitate the precursor over the support by raising the pH of the support/precursor dispersion this is achieved a base before the drying stage. The precipitation of precursors must be done in a controlled manner in order for the particles to deposit homogeneously over the clay's surface.
Also, the precursor/support dispersion is filtered before proceeding to the drying stage, and/or is separated by solid/liquid separation techniques before the drying stage. Preferably, a filtration or liquid/solid separation is done to separate the clay the metallic precursors deposited over the surface of the solution containing the metallic salt ion used, although a direct drying can be done to evaporate all the water present in the dispersion. In some cases when the separation is done by filtering to separate the clay the metallic precursors deposited, it is recommended to wash the clay to eliminate any trace of the soluble salt. The next step is the thermal treatment carried out under controlled atmosphere conditions to effect the decomposition of the metallic salts or hydroxides in the appropriate oxide, provided the precursor deposited over the clay is not said oxide; the next step is the reduction of the metal oxide in the appropriate metal. The conditions for the reduction (temperature and partial oxygen pressure) will depend on the metallic element used.
Utilizing the techniques described above, it is possible to obtain monodispersed metallic nanoparticles deposited over the support, always in a size smaller than 30 nm, and very frequently it is possible to obtain controlled sizes between 10 nm and 5 nm, and thus form a nanoparticulate “nanocomposite” material useful for a diversity of applications. Thus, when the metallic element has been selected from Cu, Ag, Au, Rh, Pd, Ir, Ni, Pt and combinations thereof, the nanoparticulate “nanocomposite” material is useful as such, or as a component of a catalyst, while when the metallic element selected is Ag, the nanoparticulate “nanocomposite” material is useful as a biocide or as a component of biocides. In the same manner, when the metallic element selected is Cu, the nanoparticulate “nanocomposite” material is useful as fungicide or as a component of fungicide products.
Also, when the metallic element has been selected from Cu, Ag, Au and combinations thereof, the nanoparticulate “nanocomposite” material is useful as component of optoelectronic materials, while when the metallic element has been selected from Fe, Ni, Co and combinations thereof the nanoparticulate “nanocomposite” material is useful as component of ferromagnetic fluids.
In this process the clay used may have any particle size, although when the nanoparticles are formed on the clay particle's surface, it is advisable to use a clay product with the smallest possible particle size in order for the surface of the particle accessible to nanoparticles formation to be the maximum possible size. In this manner the clay can be added as milled powder with a particle size smaller than 44 μm. Rheologic grade products such as rheologic grade sepiolite can also be used, as obtained by means of a wet micronization processes such as those described in the patent application EP-A-0170299, with which free acicular particles have been obtained while maintaining the high “aspect ratio” of the particles, and where the de-agglomeration process has left more free surface accessible to deposition. In addition, the colloidal properties of the clays treated according to this micronization process have higher stability and disperse better in the metallic salt dilution, allowing for a more homogenous coating.
The information described above indicates that the procedure described in the present invention is based on the deposition over the surface of these metallic salts, oxides or hydroxide clays, followed by a reduction treatment intended to obtain the corresponding metals. The reduction process is done by means of a thermal treatment carried out under controlled atmosphere conditions. It can be noted that the size of the nanoparticles formed by this process is smaller than 30 nm, and normally a size of approximately 3 nm, with a homogeneous distribution over the surface and not clustered. The nanoparticles are distributed linearly and oriented along the longitudinal axis of the microfibrous particles. A possible explanation for the formation of the metallic nanoparticles in this particular arrangement may be the transformations undergone by the sepiolite and the atapulgite during thermal treatments. At 350° C. the sepiolite losses two of the four molecules of hydration water, producing the folding of the sepiolite's structure, and the collapse of the zeolitic channels in order for the cations located at the edge of the octahedral layer of the silicate to complete their coordination with the oxygen molecules of the tetrahedral layer of the adjacent silicon. This change is reversible. The original structure can be recovered by rehydrating the sepiolite. At a temperature of 500° C., the sepiolite losses the two remaining water molecules of crystallization, and although there are no additional structural changes, the folding of the structure becomes at this point irreversible. The atapulgite suffers a similar structural change during thermal treatment. It is believed that during the thermal treatment carried out to decompose the metal salts or hydroxides in their corresponding oxides, and the subsequent step of reducing the metallic oxides particles, these particles are trapped during the folding and collapsing of the open channels located at the edge of the structures, preventing the migration of the metallic nanoparticles and their coalescence and growth processes that would form particles of greater size. As a consequence, it is possible to obtained monodispersed nanoparticles which size is smaller than 30 nm that can be controlled as a function of the impregnation conditions for the metallic salts, hydroxides and oxides, and as a function of the reduction conditions, to obtain a controlled particle size that can be maintained between 10 nm and 5 nm, and even to obtain particle sizes smaller than 5 nm. This mechanism explains the linear arrangement of the nanoparticles along the axis of the microfibrous particle, following the open channels located at the edge of the structure over the surface of the acicular particle.
This section contains the description of some examples of the embodiments of the invention that will be referred to the following figures:
a is a microphotograph of copper nanoparticles supported over sepiolite and obtained according to the method described in Example 1;
b is a less enlarged microphotograph of the nanoparticles supported over sepiolite and also obtained according to the method described in Example 1;
a is an X-ray diffractogram showing copper precipitated as gerhardite over the sepiolite support according to Example 1;
b is an X-ray diffractogram of the final product according to Example 1;
a is a microphotograph of silver nanoparticles supported over sepiolite and obtained according to the method described in Example 2.
b is a less enlarged microphotograph of the nanoparticles supported over sepiolite and obtained according to the method described in Example 2;
a is an X-ray diffractogram showing silver oxide precipitated over the sepiolite support according to Example 2;
b is an X-ray diffractogram showing the final product according to Example 2; and
a is a microphotograph of copper nanoparticles supported over atapulgite and obtained according to the method described in Example 3;
b is a less enlarged microphotograph of the nanoparticles supported over atapulgite and obtained according to the method described in Example 3;
a is an X-ray diffractogram showing copper precipitated as copper hydroxide sulphate over the atapulgite support according to Example 3.
b is an X-ray diffractogram showing the final product according to Example 3.
The procedure begins by preparing one liter of copper dissolution (28, 51 g of copper nitrate per liter), for a theoretical impregnation level of 5%. Then the dissolution is acidified to pH 2 to insure the copper salt is dissolved.
A dispersion of micronized sepiolite in water is prepared in a mixer, in which the size of 99.9% of the particles is smaller than 44 μm and the size of 95% is smaller than 5 μm. The concentration of the dispersion is 10% solids (150 g of dry sepiolite base for 1,500 g of pregel), and the dispersion mixed during 5 minutes by means of a mechanical stirrer. This predispersion of clay, which pH is approximately 9.0 is then acidified to pH 2 and then the copper dilution is added and the mixture stirred for an additional 5 minutes to ensure the contact between the dilution and the sepiolite is complete. The sepiolite dispersion in the copper dilution has a sepiolite concentration of 6%.
Later, the copper precipitates as gerhardite (Cu4 (NO3)2(OH)6) (
The sepiolite with the precursor is then subject to a reduction process in a tubular section oven with a controlled atmosphere of 10% H2/90% Ar. The oven is outfitted with a programming device to control the temperature (±1° C.). The reduction cycle entails heating the mixture in increasing intervals of 10° C./min until reaching a temperature of 500° C. that is maintained for 2 hours, followed by a free cooling period inside the oven.
As a result of this process, small copper nanoparticles are obtained over the sepiolite fibers support. The nanoparticles appear monodispersed and arranged parallel to the direction of the sepiolite fibers as can be observed in the attached microphotographs (
Finally, the calcination process, that is carried out in a H2 atmosphere, further decreases the surface until it reaches a value of 87 m2/g.
The X-ray diffractogram of the reduced sample shows that the material is indeed composed of sepiolite and metallic copper (
Additional evidence of the metallic nature of the nanoparticles thus obtained, as well as their dispersion pattern, was obtained by analyzing the diffuse reflectance spectra within the visible ultraviolet range. When a metal finely divided (of a size smaller than the wavelength) and dispersed interacts with the electromagnetic radiation, it presents a well defined frequency, a collective electron excitation phenomenon known as surface plasmon [C. F. Bohren and D. R. Huffman, “Absorption and Scattering of Light by Small Spheres”, Ed. John Wiley and Sons, New York, 1983, pages 325 on]. In the frequency at which this phenomenon occurs, it is verified that the real part of the dielectric constant of the metal is equal to minus two times the dielectric constant of the matrix (E(w)=−2Em). Since this frequency, which can be experimentally recognized by an absorption maximum, is specific to each metal, it has served us as identification of the metallic nature of the nanoparticles. In the case of copper, the experimental spectrum shows a maximum absorption at 2.2. eV (
A silver dilution containing 35.45 g of silver nitrate per liter is prepared and then acidified to pH=2 using NO3H. A sepiolite predispersion with a 10% concentration of solids is then added to the silver nitrate dilution. The sepiolite predispersion is prepared by dispersing the sepiolite during 5 minutes in a mechanical stirrer with high powered shear blades to insure a good dispersion of the clay particles. The sepiolite used in this example is a PANGEL rheologic grade sepiolite manufactured by TOLSA S. A. Once the sepiolite predispersion has been added to the silver nitrate dilution for the Ag/sepiolite relationship to be in a 15/100 ratio, the mixture is stirred at high shear setting during 5 more minutes and it is then, while still stirring, a 1M NaOH solution is added slowly until pH=12. Increasing the pH produces the precipitation of the silver precursor that is then deposited homogeneously over the sepiolite's surface. Later, the dispersion is filtered in a vacuum and oven dried at 150° C.
During this process, the BET specific surface of the sepiolite is decreased from 439 to 204 m2/g.
The sepiolite with the silver precursor (Ag2O in this particular instance) (
The particles obtained as a result of this process are elongated sepiolite particles over which small silver nanoparticles have appeared following the direction parallel to the long axis of the sepiolite fibers. An image of these particles can be seen in
Once the silver oxide particles have been reduced, the final specific surface of the powder has decreased to 112 m2/g.
The X-ray diffractogram of the reduced sample shows that the material is indeed composed of sepiolite and silver (
In the same manner as in the prior example, the optic absorption of sepiolite samples with silver was measured in Kulbeka-Munk units by means of diffuse reflectance in the visible range of ultraviolet light. In this case the plasmon was also visible, but at a higher frequency (3.4 eV) and showing an irregular aspect as it is the case for silver nanoparticles (
A copper sulfate solution containing 79.11 g of copper sulfate per liter is first prepared and then acidified by adding SO4H2 until obtaining a pH value of 2. Later a predispersion of atapulgite in which the solids concentration=10% is added. The atapulgite predispersion is prepared by dispersing the atapulgite during 5 minutes in a mechanical stirrer with high powered shear blades to insure a good dispersion of the clay particles. The atapulgite used is an ATTAGEL 40 from the Engelhard Corporation that has been micronized in wet conditions according to the procedure described in patent EP-A-0170299. Once the atapulgite predispersion has been added to the copper sulfate dilution for the Cu/atapulgite relationship to be in a 15/100 ratio, the mixture is stirred at high shear setting during 5 more minutes and, while still stirring, a 1M NaOH solution is added slowly until pH=5.5. Increasing the pH produces the precipitation of one phase of the copper hydroxide sulfate (
The atapulgite with the precursor is subjected to a reduction process in a tubular sectioned oven under controlled atmosphere conditions of 10% H2/90% Ar. The reduction cycle is a heating process in which temperature is increased at 10° C./min until reaching a final temperature of 500° C. which is maintained during 2 hours and followed by a free cooling period inside the oven.
The particles obtained as a result of this process, are copper nanoparticles supported by atapulgite fibers. In this case acicular nanoparticles appear in a parallel arrangement following the direction of the atapulgite fiber. Their size is approximately 30 nm long by a few nm wide (
The X-ray diffractogram of the reduced sample shows that the material is indeed composed of atapulgite and metallic copper (
While the invention has been described and illustrated herein by reference to the specific embodiments, various specific materials, procedures and examples, it is understood that the invention is not restricted to the particular materials, combinations of materials, and procedures selected for that purpose. Indeed, various modifications of the invention in addition to those described herein will become apparent to those skilled in the art from the foregoing description and the accompanying figures. Such modifications are intended to fall within the scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 200302396 | Oct 2003 | ES | national |
The present application is a continuation of Co-pending PCT Application No. PCT/ES2004/000441, filed on Oct. 15, 2004, which in turn, claims priority from Spanish Application Serial No. 200302396, filed on Oct. 15, 2003. Applicants claim the benefits of 35 USC §120 as to the PCT application, and priority under 35 USC §119 as to the said Spanish Application, and the entire disclosures of both applications are incorporated herein in their entireties.
| Number | Date | Country |
|---|---|---|
| 0 170 299 | Feb 1986 | EP |
| 0 454 222 | Oct 1991 | EP |
| 1 002 574 | May 2000 | EP |
| 07173022 | Jul 1995 | JP |
| Number | Date | Country | |
|---|---|---|---|
| 20060293171 A1 | Dec 2006 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/ES2004/000441 | Oct 2004 | US |
| Child | 11403140 | US |
