Title of Invention

"MG2MM'O6+X, (M=Y, LA OR A RARE EARTH METAL, AND M'=SN, SB, ZR AND TA) DIELECTRIC CERAMICS"

Abstract

This invention relates to a new group of complex ceramic oxides and a process for their production. These groups of novel complex ceramic oxides are of the general formula Mg2MM'O6+x, where M=Rare earth metal ion or Yttrium or Lanthanum and M'=Sn, Sb, Zr, Hf, Ta, and Nb; and where -0.5<x<+0.5; and have a defective pyrochlore structure. Minor variations in the compositions up to 8% in any of the metal ions may be tolerated for the formation of the required structure.

Full Text

Mg2MM'O6+x, (M = Y, rare earth metal, and WT = Sn or Zr) dielectric ceramics and their preparation as nanoparticles This invention relates to a new group of complex ceramic oxides and a process for their production. This invention particularly relates to novel complex ceramic oxides of the general formula Mg2MM'O6+x, where M = rare earth metal ion or Y and M' = Sn, Sb, Zr, Hf, Ta and Nb; having a defect pyrochlore structure and the solid state reaction method of their preparation. The complex ceramic powders of the present invention are useful for active and passive electronic applications, for temperature stable, low loss, high permitivity dielectric applications, for temperature stable and temperature compensating dielectrics; microwave dielectrics and as co-fired microwave components, for electrodes of Fuel cells, as catalyst (solid photocatalysts, oxidation catalysts), as gas monitoring sensors, as possible host for radioactive wastes and as host for fluorescence centers. Introduction In recent years, there has been a raising order of interest in the preparation and characterization of complex ceramic oxides, with the general formula A2MM'06+X; where A = Ba, Sr and Ca; M = Y and rare earths and M' = Sb, Sn, Nb, Zr, Hf and Ta. The compounds with general formula Ba2MM'O6+x crystallize in the perovskite structure. Some of the compounds with the formula Sr2MM'O6+x are also reported. They also possess the perovskite structure. Some of the compounds reported in these system are; Sr2GaNbO6, Sr2GaTaO6, Sr2AINbO6, Sr2AITaO6, Ca2GaNbO6, Ca2GaTa06l Ca2AINbO6, Ca2AITaO6, Ba2DySnO55, Ba2EuNbO6, Ba2ErSbO6, YBa2NbO6, Ba2DySbO6, Ba2PrHfO55 (J Koshy, K S Kumar, J Kurian, Y P Yadava and A D Damodaran; Rare-earth barium Stannates: Synthesis, characterization and potential use as substrate for YBa2Cu307.0; Journal of American Ceramic Society; 78[11] 5088-92 (1995); and C D Bradle and V J Fratello; preparation of perovskite oxides for high Tc superconductor substrates; Journal of Materials Research, volume-5, Number-10 pages 2160-2164 year 1990). These compounds were prepared by the conventional solid state reaction technique or by using an exothermic combustion of a polymeric precursor at a relatively low temperature. (J Koshy, J Kurian, R Jose, A M John, P K Sajith, J James, S P Pai and R Pinto; Bulletin of Material Science, Volume-22, Number-3 May 1999 pages 243-249; A M John, R Jose and J Koshy; Synthesis and rapid densification of nanoparticles of Barium Praseodymium Hafnium Oxide; a complex perovskite; Journal of Nanoparticle research, volume-3 year 2001 pages 413-417). However in case of Ca2MM'O6+x compounds apart from the perovskite structure, a few cases of meta stable pyrochlore structures were also reported. These meta stable pyrochlores transformed into perovskite structures at about 650-700°C. (J Koshy, J Kurian, R Jose, Asha M John, P K Sajith, J James, S P Pai and R Pinto "Novel ceramic substrate for high Tc superconductors" Bulletin of Material Science, vol. 22, pp243-249 (1999); S Ya Istomin, O G D'yachenko and E V Antipov, Synthesis and characterization of reduced niobates CaLnNb2O7, Ln = Y Nd with pyrochlore structure; Materials Research Bulletin, vol. 32, No. 4, pp421- 30, (1997); J Koshy, J Kurian, P K Sajith, K S Kumar, R Jose, Asha M John and A D Damodaran; Novel ceramic substrate for Bi-cuperate superconductors; US patent No. 5,741,747 dated April 21, (1998)). Some of the magnesium bearing ceramic oxides reported for possible use in electronic ceramic applications are Sr2MgMoO6, La2MgTiO6, Gd2MgTiO6, Gd2MgZr06 and La2MgGeO6, (C D Bradle and V J Fratello, preparation of perovskite oxides for high Tc superconductor substrates; journal of Materials Research, volume-5, Number-10, pages-2160-2164 year 1990;). Most of the above mentioned compounds had a perovskite structure. However some of the Magnesium bearing compounds that were reported are Ba(Mg1/3Ta2/3)O3 and PbMg1/3Nb2/3O3 and Bi2M'2/3M"4/3O7 where M' = Zn, Mg, Ni Sc, In and Cu and M" = Nb and Ta (M valant and P K Davis; Synthesis and dielectric properties of pyrochlore solid solutions in the Bi203-ZnO-Nb2O5-TiO2 system, Journal of Materila Science 34 (1999) 5437-5442). Some of these magnesium-bearing compounds had pyrochlore structures. However compounds of the type Mg2MM'O6+x, either with perovskite structure or pyrochlore structure were not reported. Pyrochlore structures are the structures with the general formula A2B2O7, where A atoms are 8 coordinated ad B atoms are 6 coordinated with one extra O-atom. In recent years many pyrochlore compounds with more complicated composition (AA')2(BB)2O7 have been synthesized. For the possibility of existence of any pyrochlore compound, there are two criteria: (1) the ratio of the ionic radius of the cation at the A site to that at the B site must be between 1.46 and 1.80 and (2) the chemical valencies of the various ions must made the compound neutral. (Y Xuan, R Liu and Y Q Jia; Synthesis of a new series of compounds RE2Co2/3Nb4/3O7 and stability field diagram of RE2B2/3'B4/3"O7 pyrochlore compounds; Materials Chemistry and Physics, vol-53, pp256-261 (1998)). Pyrochlore compounds have been extensively studied over the past because of their specific properties and consequent technological applications. Some of the very important properties of members of this group of compounds are: low thermal conductivity, high melting point, high thermal expansion coefficient, high stability. They can be used in Gas turbines and diesel engines as thermal barrier coatings. Some of the pyrochlore compounds exhibit high Ionic conductivity and can be used as electrodes for Fuel cells, egs, Gd2TiMoO7+x; Gd2TiO7+x (P Holtappels, F W Poulsen and M Mogensen; Electrical conductivities and chemical stabilities of mixed conducting pyrochlores for Solid oxide fuel cell applications; Solid State Ionics, vol. 135, pp 675-679 (2000)). Pyrochlore oxides also exhibit catalytic properties and are used as solid photocatalysts (eg. Bi2MNbO7, M-AI, Ga, In) (Zhigang Zou, Jinhua Ye and Hironori Arakawa, Preparation, structural and optical properties of a new class of compounds, Bi2MNbO7 (M = Al, Ga In); Materials Science and Engineering vol. B79, pp83-85 (2001)), oxidation catalysts and as gas monitoring sensors. They have the ability to accommodate defects and act as possible host for radioactive wastes, and as host for fluorescence centers. Some of the pyrochlore materials also show superconductivity and magnetic properties, including Colossal Magneto resistant behavior; e.g. Sm2Ti2O7, La2Zr2O7, Nd2Zr2O7, La07Bao.3MnO3, (L Li, Y W Song, H Xiong, Y Q Jia, N Matsushita and Y Xuan; Synthesis, crystal structure and magnetic properties of Sm2.xCox Ti2.YNby07 (x = 0, 0.2, 0.4); Materials Chemistry ad Physics, vol-9273, pp. 1-7 (2002); K Koteswara Rao, Taqveem Banu, M Vital, G Y S K Swamy and K Ravi Kumar; Preparation and characterization of bulk and nanoparticles of La2Zr2O7 and Nd2Zr207 by sol-gel method; Materials letters; vol. 54, pp 205-210 (2002)). Pyrochlores have been used in active and passive electronic applications. They are recently recognized as potential candidates for temperature stable, low loss, high permitivity dielectric applications and in temperature stable and temperature compensating dielectrics; microwave dielectrics and as co-fired microwave components (P Holtappels, F W Poulsen and M Mogensen; Electrical conductivities and chemical stabilities of mixed conducting pyrochlores for SOFC applications,; Solid State Ionics, vol. 135, pp 675-679 (2000)). However no compound of the formula Mg2MM'O6+x (where - 0.5 ions; and M' = Sb, Sn, Zr, & Ta) has been reported till now. Objectives The main objectives of the present invention is to provide a novel Magnesium based class of complex ceramic oxides, that could be used (i) for active and passive electronic applications, (ii) for temperature stable, low loss, high permitivity dielectric applications (iii) for temperature stable and temperature compensating dielectrics; microwave dielectrics and as co-fired microwave components (iv) for electrodes for Fuel cells (v) as catalyst (solid photocatalysts, oxidation catalysts) (vi) as gas monitoring sensors, (vii) as possible host for radioactive wastes, and (viii) as host for fluorescence centers. Another objective of the present invention is to prepare a novel class of complex ceramic oxides having the formula Mg2MM'O6H.x where M = Y, La and rare earth metal ions; and M' = Sb, Sn, Zr, and Ta and having a defect pyrochlore structure. Yet another objective of the present invention is to provide a method for the preparation of a novel magnesium bearing class of complex ceramic oxides having the above formula, structure and uses. Invention We have now prepared a new class of Mg bearing compounds with the general formula Mg2MM'O6+x, (M = Y, La and rare earth metal ions; and M' = Sb, Sn, Zr, and Ta) having a defect pyrochlore structures. Accordingly the invention provides a process for the preparation of the above mentioned class of compounds which comprises: (i) Mixing the compounds of magnesium, M and M' (where M may be Yttrium, or any of the rare earth metals; ad M' = Antimony, Tin, Zirconium or tantalum) in such a way as to get the molar ratio of Mg:M:M' as 2:1:1 required for the formation of the compounds of the general formula Mg2MM'O6+x Minor variations in the compositions up to 8% in one metal ions may be tolerated for the formation of the required phase. (ii) The compounds employed in step (i) may be selected from their oxides, carbonates, chlorides, alkoxides, nitrates, sulphates etc; preferably the salts used are selected from oxides or carbonates. The mixture obtained in step (i) may be ball milled or mixed with wetting medium. The wetting medium may be water, alcohol, acetone or any other organic solvent. The resultant ball milled slurry may be dried to remove the liquid and obtain dry powder. (iv) Heating the resultant mixture to a temperature in the range 1000- 1450°C as required for different duration ranging from 3 hour to 50 hours, either in a single step or by taking out the reactant after few hours of heating, checking for phase formation and heating it again after grinding if necessary. Up to a maximum of 5 intermediate grindings may be required. The complex ceramic powders of the present invention are useful (i) for active and passive electronic applications, (ii) for temperature stable, low loss, high permitivity dielectric applications (iii) for temperature stable and temperature compensating dielectrics; microwave dielectrics and as co-fired microwave components (iv) for electrodes for Fuel cells (v) as catalyst (solid photocatalysts, oxidation catalysts) (vi) as gas monitoring sensors, (vii) as possible host for radioactive wastes, and (viii) as host for fluorescence centers. The details of the present invention are described in the examples given below. These examples are provided by way of illustration only and should not be construed to limit the scope of the invention. Accordingly, the present invention provides novel compounds of the general formula Mg2MM'O6+x where M = Y, La or a rare earth metal, M' = Sn, Sb, Zr and Ta, 0.5 minor variations in the compositions up to 8%, in any of the metal ions is tolerated for the formation of the required phase, and, a process for the preparation of the said novel compounds comprising: (i) Mixing the compounds of magnesium, M and M' (where M = Y, La or a rare earth metal, M' = Sn, Sb, Zr and Ta) in such a way as to get the molar ratio of Mg:M:IVr as 2:1:1 required for the formation of the compounds of the general formula Mg2MM'06+x, wherein minor variations in the compositions up to 8% in any of metal ion is tolerated for the formation of the required phase; (ii) the mixture obtained in step (i) is ball milled or mixed with a wetting medium; (iii) the resultant ball milled slurry obtained is dried to remove the liquid and obtain dry powder. (iv) Heating the resultant mixture to a temperature in the range 1000- 1600°C as required for different duration ranging from 3 hour to 50 hours, either in a single step or by taking out the reactant after few hours of heating, checking for phase formation and heating it again after grinding if necessary, upto a maximum of 5 intermediate grindings may be required. In an embodiment of the present invention, the compounds employed in the process are selected from their oxides, carbonates chlorides, alkoxides, nitrates, sulfates etc. and preferably the salts used are selected from oxides or carbonate. In another embodiment of the present invention the wetting medium used in the process is selected from water, alcohol, acetone or any other organic solvent. In another embodiment of the present invention, novel compound obtained is of the formula Mg2SmTaO6 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In still another embodiment of the present invention, novel compound obtained is of the formula Mg2NdTaO6 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In yet another embodiment of the present invention, novel compound obtained is of the formula Mg2DyTaO6 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In yet another embodiment of the present invention, novel compound obtained is of the formula Mg2PrTa06 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In yet another embodiment of the present invention, novel compound obtained is of the formula Mg2GdTaO6 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In still another embodiment of the present invention, novel compound obtained is for the formula Mg2EuTa06 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In still another embodiment of the present invention, novel compound obtained is of the formula Mg2LaTaO6 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In further embodiment of the present invention, novel compound obtained is of the formula Mg2DySb06 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In further embodiment of the present invention, novel compound obtained is of the formula Mg2SmZrO5 5 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In still further embodiment of the present invention, novel compound obtained is of the formula Mg2NdZr05 5 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In still embodiment of the present invention, novel compound obtained is of the formula Mg2DyZrO5 5 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In yet further embodiment of the present invention, novel compound obtained is of the formula Mg2LaSnO5 5 as nanoparticle having pyrochlore structure wherein minor variation in the composition upto 8% in any of the metal ions is tolerated for the formation of the phase. In yet further embodiment of the present invention, novel compound obtained is of the formula Mg2GdZrO5 5 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In still another embodiment of the present invention, novel compound obtained is of the formula Mg2EuZr055 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In yet another embodiment of the present invention, novel compound obtained is of the formula Mg2l_aZrO5 5 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. In still further embodiment of the present invention, novel compound obtained is of the formula Mg2PrZrO5 5 as nanoparticle having pyrochlore structure wherein minor variation in the compositions upto 8% in any of the metal ions is tolerated for the formation of the phase. Example-1 : Magnesium Samarium Tantaiate (Mg2SmTaO6), Magnesium Samarium Tantaiate (Mg2SmTaO6), for example, is obtained by: (i) Taking four gram molecular weight of Magnesium Carbonate (MgCO3), one gram molecular weight of Samarium Oxide (Sm2O3), and one gram molecular weight of Tantalum oxide (Ta205). (ii) Mixing these three reactants by ball milling the mixture for 24 hours using water as the wetting medium. (iii) Drying the ball milled reaction mixture (sample) in an oven at about 120°C. (iv) Pelletizing the sample and heating at 1400°C for 10 hours with three intermediate grinding. (v) The XRD pattern of this compound is shown in Figure-1. (vii) Considering the highest possible oxidation states of the metals used; (Mg -+2, Sm - +3 and Ta - +5) the chemical formula of the compound Magnesium Samarium Tantalate is worked out to be Mg2SmTaO6. (vii) The variation of dielectric constant and loss factor of the compound Mg2SmTaO6 is shown in Figure - 2 and Figure - 3. This clearly shows that the compound is suitable for use as electronic ceramic material for all applications where the dielectric constant plays a crucial role. E.g. substrate for superconductors. (viii) The compound does not show any phase transition on heating up to 1300°C. Kample-2 Magnesium Lanthanum Stanate (Mg2LaSnO5 5), Magnesium Lanthanum Stanate (Mg2LaSnO55), for example, is jtained by; (i) Taking four gram molecular weight of Magnesium Carbonate (MgCO3), one gram molecular weight of lantanum oxide(La2O3), and one gram molecular weight of Tin oxide (SnO2). (ii) Mixing these three reactants by ball milling the mixture for 12 hours using water as the wetting medium. (iii) Drying the ball milled reaction mixture (sample) in an oven at about 120°C (iv) Pelletizing the sample and heating at 1450°C for 10 hours with one intermediate grinding. (v) The XRD pattern of this compound is shown in Figure-4. (vi) Considering the highest possible oxidation states of the metals used; (Mg -+2, La - +3 and Sn - +4) the chemical formula of the compound Magnesium lanthanum Stannate is worked out to be (Mg2LaSn05 5), (vii) The variation of dielectric constant and loss factor of the compound Mg2LaSnO5 5 is shown in Figure - 5 and Figure - 6. This clearly shows that the compound is suitable for use as electronic ceramic material for all applications where dielectric constant and loss factor play an important role. E.g. as substrate for superconductors. (viii) The compound does not show any phase transition on heating up to 1300°C. Example-3 Magnesium Dysprosium Antimonate (Mg2DySbO6), Magnesium Dysprosium Antimonate (Mg2DySbO6), for example, is obtained by; (i) Taking four gram molecular weight of Magnesium Carbonate (MgC03), one gram molecular weight of dysprosium oxide (Dy203), and one gram molecular weight of antimony pentoxide (Sb2O5). (ii) Mixing these three reactants by ball milling the mixture for 18 hours using water as the wetting medium. (iii) Drying the ball milled reaction mixture (sample) in an oven at about 120°C (iv) Pelletizing the sample and heating at 1550°C for 10 hours with one intermediate grinding. (v) The XRD pattern of this compound is shown in Figure-7. (vi) Considering the highest possible oxidation states of the metals used; (Mg -+2, Dy - +3 and Sb - +5) the chemical formula of the compound Magnesium Dysprosium Antimonate is worked out to be (Mg2DySbO6), (vii) The variation of dielectric constant and loss factor of the compound Mg2DySbO6 is shown in Figure-8 and Figure-9. This clearly shows that the compound is suitable for use in all electronic ceramic applications where the dielectric constant and loss factor plays an important role as substrate for superconductors. (viii) The compound does not show any phase transition on heating up to 1300°C. Example-4 Magnesium Neodymium Zirconate (Mg2NdZrO6), Magnesium Neodymium Zirconate (Mg2NdZrO6), for example, is obtained by; (i) taking four gram molecular weight of Magnesium Carbonate (MgCO3), one gram molecular weight of Neodymium oxide (Nd203), and one gram molecular weight of Zirconium oxide (Zr02). (ii) mixing these three reactants by ball milling the mixture for 15 hours using water as the wetting medium. (iii) Drying the ball milled reaction mixture (sample) in an oven at about 120°C (iv) Pelletizing the sample and heating at 1450°C for 8 hours with one intermediate grinding and subsequent heating. (v) The XRD pattern of this compound is shown in Figure-10. (vi) Considering the highest possible oxidation states of the metals used; (Mg -+2, Nd - +4 and Zr - +4) the chemical formula of the compound Magnesium Presudomium zirconate is worked out to be (Mg2NdZrO6), (vii) The variation of dielectric constant and loss factor of the compound Mg2NdZrO6 is shown in Figure - 11 and Figure- 12. This clearly shows that the compound is suitable for use in all electronic ceramic applications where dielectric constant and loss factor plays an important role. E.g. as substrate for superconductors. (viii) The compound does not show any phase transition on heating up to 1300°C. We claim: 1. Mg2MM'06+x,(M=Y,La or a rare earth metal, and M-Sn, Sb, Zr and Ta) dielectric ceramics, -0.5 2. Compounds as claimed in claim 1, of the formula Mg2SmTaO6 as nanoparticles,having pyrochlore structure wherein minor variation in the compositions up to 8% in any of the metal ions is tolerated for the formation of the structure. 3. Compounds as claimed in claim 1, of the formula Mg2SmTaO6 as nanoparticles, having pyrochlore structure wherein minor variation in the compositions up to 8% in any of the metal ions is tolerated for the formation of the structure. 4. Compounds as claimed in claim 1, of the formula Mg2SmTaO6 as nanoparticles, having pyrochlore structure wherein minor variation in the compositions up to 8% in any of the metal ions is tolerated for the formation of the structure. 5. Compounds as claimed in claim 1, of the formula Mg2SmTaO6 as nanoparticles, having pyrochlore structure wherein minor variation in the compositions up to 8% in any of the metal ions is tolerated for the formation of the structure. 6. Compounds as claimed in claim 1, of the formula Mg2SmTaO6as nanoparticles, having pyrochlore structure wherein minor variation in the compositions up to 8% in any of the metal ions is tolerated for the formation of the structure. 7. Compounds as claimed in claim 1, of the formula Mg2SmTaO6as nanoparticles, having pyrochlore structure wherein minor variation in the compositions up to 8% in any of the metal ions is tolerated for the formation of the structure. 8. Compounds as claimed in claim 1, of the formula Mg2SmTaO6 as nanoparticles, having pyrochlore structure wherein minor variation in the compositions up to 8% in any of the metalions is tolerated for the formation of the structure. 9. Compounds as claimed in claim 1, of the formula Mg2SmTaO6 as nanoparticles, having pyrochlore structure wherein minor variation in the compositions up to 8% in any of the metal ions is tolerated for the formation of the structure. 10. A process for the preparation of the class of compounds as claimed in claim 1, the said process comprising: (i) mixing the compounds of magnesium, M and M' (where M=Y, La or a rare earth metal, M-Sn, Sb, Zr and Ta) in such a way as to get the molar ratio of Mg:M:M' as 2:1:1 required for the formation of the required structure; (ii) the mixture obtained in step (i) is ball milled together with a wetting medium; (iii) the resultant ball milled slurry obtained is dried to remove the liquid and obtain a dry powder; (iv) heating the above said mixture to a temperature in the range of 1000-1600°C as required for different durations ranging from 3 hours to 50 hours, either in a single step or by taking out the reactant after heating, checking for phase formation and heating it again after grinding if necessary, upto a maximum of 5 intermediate grindings may be required. 11. A process as claimed in claim 10, wherein the compounds employed in step (i) are selected from the group consisting of their oxides, carbonates chlorides, alkoxides, nitrates, sulfates etc. and preferably the salts used are selected from oxides or carbonate. 12. A process as claimed in claim 10, wherein the wetting medium used in step (ii) is selected from water, alcohol, acetone or any other organic solvent. 13. Mg2MM'O6+x, (M=Y, La or a rare earth metal, and M'=Sn, Sb, Zr and Ta) dielectric ceramics substantially as herein described with references to the examples.

Documents:

3245-DELNP-2004-Abstract (06-05-2009).pdf

3245-delnp-2004-abstract.pdf

3245-DELNP-2004-Claims (06-05-2009).pdf

3245-delnp-2004-claims.pdf

3245-delnp-2004-correspondence-oters.pdf

3245-DELNP-2004-Correspondence-Others-(06-05-2009).pdf

3245-DELNP-2004-Description (Complete) (06-05-2009).pdf

3245-delnp-2004-description (complete).pdf

3245-delnp-2004-drawings.pdf

3245-DELNP-2004-Form-1 (06-05-2009).pdf

3245-delnp-2004-form-1.pdf

3245-delnp-2004-form-18.pdf

3245-DELNP-2004-Form-2 (06-05-2009).pdf

3245-delnp-2004-form-2.pdf

3245-DELNP-2004-Form-3 (19-05-2009).pdf

3245-DELNP-2004-Form-3- (06-05-2009).pdf

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3245-delnp-2004-form-5.pdf

3245-DELNP-2004-Petition-137-(19-05-2009).pdf